Quinazoline(di)ones for invertebrate pest control

ABSTRACT

Compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, are disclosed which are useful as invertebrate pest control agents 
                         
wherein A, B, J, K, L and R 3  are as defined in the disclosure.
 
     Also disclosed are compositions for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I an N-oxide thereof or a suitable salt thereof and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. 
     Also disclosed are methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I, its N-oxide or a suitable salt of the compound (e.g., as a composition described herein).

BACKGROUND OF THE INVENTION

This invention relates to certain quinazoline(di)ones, their N-oxides,agriculturally suitable salts and compositions thereof, and a method ofuse for controlling invertebrate pests in both agronomic andnonagronomic environments.

The control of invertebrate pests is extremely important in achievinghigh crop efficiency. Damage by invertebrate pests to growing and storedagronomic crops can cause significant reduction in productivity andthereby result in increased costs to the consumer. The control ofinvertebrate pests in forestry, greenhouse crops, ornamentals, nurserycrops, stored food and fiber products, livestock, household, and publicand animal health is also important. Many products are commerciallyavailable for these purposes, but the need continues for new compoundsthat are more effective, less costly, less toxic, environmentally saferor have different modes of action.

WO01/070671 discloses N-acyl anthranilic acid derivatives of Formula ias arthropodicides

wherein, inter alia, A and B are independently O or S; J is anoptionally substituted phenyl ring, 5- or 6-membered heteroaromaticring, naphthyl ring system or an aromatic 8-, 9- or 10-membered fusedheterobicyclic ring system; R¹ and R³ are independently H or optionallysubstituted C₁-C₆ alkyl; R² is H or C₁-C₆ alkyl; each R⁴ isindependently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, halogen or CN; and n is 1to 4.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula I including allgeometric and stereoisomers, their N-oxides and suitable salts thereof,

wherein

-   -   A and B are independently O or S;    -   J is a phenyl ring, a naphthyl ring system, a 5- or 6-membered        heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused        heterobicyclic ring system wherein each ring or ring system is        optionally substituted with 1 to 4 substituents independently        selected from R⁵;    -   K is, together with the two contiguous linking carbon atoms, a        fused phenyl, a fused pyridinyl or a fused pyrimidinyl ring        selected from the group consisting of K-1, K-2, K-3, K-4, K-5        and K-6, each optionally substituted with 1 to 4 substituents        independently selected from R⁴

-   -   L is a direct bond; or a linking chain of 1 to 3 members        selected from carbon, nitrogen, oxygen and sulfur, optionally        including one or two chain members as C(=E), SO or S(O)₂, and        optionally substituted with one to three substituents        independently selected from R¹³;    -   E is O, S or NR⁸;    -   R³ is H; G; C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, each optionally substituted with 1 to 5 substituents        independently selected from the group consisting of G, halogen,        CN, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄        alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkylcarbonyl, C₃-C₆ trialkylsilyl,        phenyl, phenoxy and 5- or 6-membered heteroaromatic ring, each        phenyl, phenoxy and 5- or 6-membered heteroaromatic ring        optionally substituted with one to three substituents        independently selected from R⁶; or phenyl optionally substituted        with 1 to 3 substituents independently selected from R⁶;    -   G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic        ring, optionally including one or two ring members selected from        the group consisting of C(═O), SO and S(O)₂ and optionally        substituted with 1 to 4 substituents independently selected from        R¹²;    -   each R⁴ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl,        C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, NO₂,        hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄        alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄        haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino,        C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₁-C₄ alkoxyalkyl,        C₁-C₄ hydroxyalkyl, C(O)R¹⁰, CO₂R¹⁰, C(O)NR¹⁰R¹¹, NR¹⁰R¹¹,        N(R¹¹)CO₂R¹⁰ or C₃-C₆ trialkylsilyl; or    -   each R⁴ is independently a phenyl, benzyl, phenoxy or a 5- or        6-membered heteroaromatic ring, each ring optionally substituted        with one to three substituents independently selected from R⁶;    -   each R⁵ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl,        C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H,        CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄        alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄        alkylsulfonyloxy, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl,        C₁-C₄ haloalkylsulfonyl, C₁-C₄ haloalkylsulfonyloxy, C₁-C₄        alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl,        C₃-C₈ dialkylaminocarbonyl or C₃-C₆ trialkylsilyl; or    -   each R⁵ is independently a phenyl, benzyl, benzoyl, phenoxy, 5-        or 6-membered heteroaromatic ring or an aromatic 8-, 9- or        10-membered fused heterobicyclic ring system, each ring or ring        system optionally substituted with one to three substituents        independently selected from R⁶; or    -   two R⁵ groups when attached to adjacent carbon atoms are taken        together as —OCF₂O—, —CF₂CF₂O— or —OCF₂CF₂O—;    -   each R⁶ is independently C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄        alkynyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl,        C₂-C₄ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, NO₂, C₁-C₄        alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl,        C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄        haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino,        C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₃-C₆        (alkyl)cycloalkylamino, C₂-C₄ alkylcarbonyl, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-C₈        dialkylaminocarbonyl or C₃-C₆ trialkylsilyl;    -   R⁸ is H; C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl or C₃-C₆        cycloalkyl, each optionally substituted with 1 to 5 substituents        independently selected from the group consisting of halogen, CN,        NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio,        C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₂-C₆ alkoxycarbonyl,        C₂-C₆ alkylcarbonyl, C₃-C₆ trialkylsilyl, a phenyl ring and a 5-        or 6-membered heteroaromatic ring, each ring optionally        substituted with one to three substituents independently        selected from R⁶; CN; NO₂; C₂-C₆ alkoxycarbonyl; C₁-C₄        alkylsulfonyl; or phenyl or phenylsulfonyl optionally        substituted with 1 to 3 substituents independently selected from        R⁶;    -   each R¹⁰ is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   each R¹¹ is independently H or C₁-C₄ alkyl;    -   each R¹² is independently C₁-C₂ alkyl, halogen, CN, NO₂ or C₁-C₂        alkoxy;    -   each R¹³ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen,        CN, COOH, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₆ alkoxycarbonyl,        C₂-C₆ alkoxycarbonylalkyl; or    -   each R¹³ is a phenyl or a 5- or 6-membered heteroaromatic ring,        each ring optionally substituted with one to three substituents        independently selected from R⁶; and    -   n is 0,1,2,3 or 4.

This invention also pertains to a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of Formula I, its N-oxideor a suitable salt of the compound (e.g., as a composition describedherein). This invention also relates to such a method wherein theinvertebrate pest or its environment is contacted with a biologicallyeffective amount of a compound of Formula I or a composition comprisinga compound of Formula I and a biologically effective amount of at leastone additional compound or agent for controlling invertebrate pests.

This invention also pertains to a composition for controlling aninvertebrate pest comprising a biologically effective amount of acompound of Formula I, its N-oxide or a suitable salt of the compoundand at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent. This inventionalso pertains to a composition comprising a biologically effectiveamount of a compound of Formula I, its N-oxide or a suitable salt of thecompound and an effective amount of at least one additional biologicallyactive compound or agent.

DETAILS OF THE INVENTION

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy”includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy andthe different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl”denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” includeCH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers. “Alkylsulfinyl” includes bothenantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl”include CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O), (CH₃)₂CHS(O) and thedifferent butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.Examples of “alkylsulfonyl” include CH₃S(O)₂, CH₃CH₂S(O)₂,CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂ and the different butylsulfonyl,pentylsulfonyl and hexylsulfonyl isomers. Examples of “alkylsulfonyloxy”include CH₃S(O)₂O, CH₃CH₂S(O)₂O, CH₃CH₂CH₂S(O)₂O, (CH₃)₂CHS(O)₂O and thedifferent butylsulfonyloxy, pentylsulfonyloxy and hexylsulfonyloxyisomers. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”,“alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”,and the like, are defined analogously to the above examples.“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl,cyclopentyl, and cyclohexyl.

“Aromatic” indicates that each of ring atoms is essentially in the sameplane and has a p-orbital perpendicular to the ring plane, and in which(4n+2) π electrons, when n is 0 or a positive integer, are associatedwith the ring to comply with Hückel's rule. The term “aromatic ringsystem” denotes fully unsaturated carbocycles and heterocycles in whichat least one ring of a polycyclic ring system is aromatic. The term“aromatic carbocyclic ring or ring system” includes fully aromaticcarbocycles and carbocycles in which at least one ring of a polycyclicring system is aromatic (e.g. phenyl and naphthyl). The term “aryl”refers to any optionally substituted aromatic ring or ring system. Theterm “nonaromatic carbocyclic ring or ring system” denotes fullysaturated carbocycles as well as partially or fully unsaturatedcarbocycles where the Hückel rule is not satisfied by any of the ringsin the ring system. The term “hetero” in connection with rings or ringsystems refers to a ring or ring system in which at least one ring atomis not carbon and which can contain 1 to 4 heteroatoms independentlyselected from the group consisting of nitrogen, oxygen and sulfur,provided that each ring contains no more than 4 nitrogens, no more than2 oxygens and no more than 2 sulfurs. The term “heteroaromatic ring orring system” includes fully aromatic heterocycles and heterocycles inwhich at least one ring of a polycyclic ring system is aromatic (wherearomatic indicates that the Hückel rule is satisfied). The term“nonaromatic heterocyclic ring or ring system” denotes fully saturatedheterocycles as well as partially or fully unsaturated heterocycleswhere the Hückel rule is not satisfied by any of the rings in the ringsystem. The heterocyclic ring or ring system can be attached through anyavailable carbon or nitrogen by replacement of a hydrogen on said carbonor nitrogen.

The term “halogen”, either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” include F₃C, ClCH₂, CF₃CH₂ andCF₃CCl₂. The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”,“haloalkylthio”, and the like, are defined analogously to the term“haloalkyl”. Examples of “haloalkenyl” include (Cl)₂C═CHCH₂ andCF₃CH₂CH═CHCH₂. Examples of “haloalkynyl” include HC≡CCHCl, CF₃C≡C,CCl₃C≡C and FCH₂C≡CCH₂. Examples of “haloalkoxy” include CF₃O, CCl₃CH₂O,HCF₂CH₂CH₂O and CF₃CH₂O. Examples of “haloalkylthio” include CCl₃S,CF₃S, CCl₃CH₂S and ClCH₂CH₂CH₂S. Examples of “haloalkylsulfinyl” includeCF₃S(O), CCl₃S(O), CF₃CH₂S(O) and CF₃CF₂S(O). Examples of“haloalkylsulfonyl” include CF₃S(O)₂, CCl₃S(O)₂, CF₃CH₂S(O)₂ andCF₃CF₂S(O)₂. Examples of “haloalkylsulfonyloxy” include CF₃S(O)₂O,CCl₃S(O)₂O, CF₃CH₂S(O)₂O and CF₃CF₂S(O)₂O.

Examples of “alkylcarbonyl” include C(O)CH₃, C(O)CH₂CH₂CH₃ andC(O)CH(CH₃)₂. Examples of “alkoxycarbonyl” include CH₃OC(═O),CH₃CH₂OC(═O), CH₃CH₂CH₂OC(═O), (CH₃)₂CHOC(═O) and the different butoxy-or pentoxycarbonyl isomers. Examples of “alkoxycarbonylalkyl” includeCH₃OC(═O)CH₂, CH₃CH₂OC(═O)CH₂, CH₃CH₂CH₂OC(═O)CH₂CH₂ and(CH₃)₂CHOC(═O)CH₂. Examples of “alkylaminocarbonyl” include CH₃NHC(═O),CH₃CH₂NHC(═O), CH₃CH₂CH₂NHC(═O), (CH₃)₂CHNHC(═O) and the differentbutylamino- or pentylamincarbonyl isomers. Examples of“dialkylaminocarbonyl” include (CH₃)₂NC(═O), (CH₃CH₂)₂NC(═O),CH₃CH₂(CH₃)NC(═O), CH₃CH₂CH₂(CH₃)NC(═O) and (CH₃)₂CHN(CH₃)C(═O).

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 6. Forexample, C₁-C₃ alkylsulfonyl designates methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄alkoxyalkyl designates the various isomers of an alkyl group substitutedwith an alkoxy group containing a total of four carbon atoms, examplesincluding CH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

In the above recitations, when a compound of Formula I is comprised ofone or more heterocyclic rings, all substituents are attached to theserings through any available carbon or nitrogen by replacement of ahydrogen on said carbon or nitrogen.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents. Further, when the subscript indicates arange, e.g. (R)_(i-j), then the number of substituents may be selectedfrom the integers between i and j inclusive.

The term “optionally substituted with one to three substituents” and thelike indicates that one to three of the available positions on the groupcan be substituted. When a group contains a substituent which can behydrogen, for example R³ or R⁸, then, when this substituent is taken ashydrogen, it is recognized that this is equivalent to said group beingunsubstituted.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. Accordingly, the present invention comprises compoundsselected from Formula I, N-oxides and agriculturally suitable saltsthereof. The compounds of the invention may be present as a mixture ofstereoisomers, individual stereoisomers, or as an optically active form.

One skilled in the art will appreciate that not all nitrogen containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethydioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

The salts of the compounds of the invention include acid-addition saltswith inorganic or organic acids such as hydrobromic, hydrochloric,nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic,malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic orvaleric acids. The salts of the compounds of the invention also includethose formed with organic bases (e.g., pyridine, ammonia, ortriethylamine) or inorganic bases (e.g., hydrides, hydroxides, orcarbonates of sodium, potassium, lithium, calcium, magnesium or barium)when the compound contains an acidic group such as a carboxylic acid orphenol.

As noted above, J is a phenyl ring, a naphthyl ring system, a 5- or6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-memberedfused heterobicyclic ring system wherein each ring or ring system isoptionally substituted with 1 to 4 substituents independently selectedfrom R⁵. The term “optionally substituted” in connection with these Jgroups refers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. An example of phenyloptionally substituted with 1 to 4 R⁵ is the ring illustrated as U-1 inExhibit 1, wherein R^(v) is R⁵ and r is an integer from 0 to 4. Anexample of a naphthyl group optionally substituted with 1 to 4 R⁵ isillustrated as U-85 in Exhibit 1, wherein R^(v) is R⁵ and r is aninteger from 0 to 4. Examples of 5- or 6-membered heteroaromatic ringsoptionally substituted with 1 to 4 R⁵ include the rings U-2 through U-53illustrated in Exhibit 1 wherein R^(v) is R⁵ and r is an integer from 0to 4. Note that J-1 through J-13 below also denote 5- or 6-memberedheteroaromatic rings. Note that U-2 through U-20 are examples of J-1,U-21 through U-35 and U-40 are examples of J-2, U-36 through U-39 areexamples of J-3, U-41 through U-48 are examples of J-4 and U-49 throughU-53 are examples of J-5. Note that U-11 is equivalent to J-6, U-26 isequivalent to J-7 or J-10, U-42 is equivalent to J-8, U-45 is equivalentto J-9, U-4 is equivalent to J-11 and U-24 is equivalent to J-12 orJ-13. Also note that in J-6 through J-13 that R⁷ and R⁹ are subsets ofR⁵ of Formula I. Examples of aromatic 8-, 9- or 10-membered fusedheterobicyclic ring systems optionally substituted with 1 to 4substituents independently selected from R⁵ include U-54 through U-84illustrated in Exhibit 1 wherein R^(v) is R⁵ of Formula I and r is aninteger from 0 to 4.

R^(v) is attached to these rings through any available carbon ornitrogen by replacement of a hydrogen on said carbon or nitrogen Notethat some U groups can only be substituted with less than 4 R^(v) groups(e.g. U-16 through U-21 and U-32 through U-34 can only be substitutedwith one R^(v)). Note that when the attachment point between (R^(v))_(r)and the U group is illustrated as floating, (R^(v))_(r) can be attachedto any available carbon or nitrogen of the U group. Note that when theattachment point on the U group is illustrated as floating, the U groupcan be attached to the remainder of Formula I through any availablecarbon or nitrogen of the U group by replacement of a hydrogen atom.

As noted above K is, together with the two contiguous linking carbonatoms, a fused phenyl, a fused pyridinyl ring or a fused pyrimidinylring optionally substituted with 1 to 4 substituents independentlyselected from R⁴. The term “optionally substituted” in connection withthese K groups refers to groups which are unsubstituted or have at leastone non-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. Examples of such Kgroups include the rings illustrated as K-1 through K-6 in Exhibit 2.Note that K-2 through K-5 can be optionally substituted with one tothree substituents independently selected from R⁴. Also note that K-6can be optionally substituted with one to two substituents independentlyselected from R⁴. In the exemplified K groups, the upper right bond isattached through the available linking carbon atom to the nitrogen atomof the N(L)-C(=A)J portion of Formula I and the lower right bond isattached through the available linking carbon atom to the carbon atom ofthe C(═B)N(L)R³ portion of Formula I. The wavy line indicates that theK-ring is attached to the remainder of Formula I as illustrated below.

Preferred K-rings are K-1, K-2, K-5 and K-6. Most preferred is K-1.

As noted above, L is a direct bond; or a linking chain of 1 to 3 membersselected from carbon, nitrogen, oxygen and sulfur, optionally includingone or two chain members as C(=E), SO or S(O)₂, and optionallysubstituted with one to three substituents independently selected fromR¹³. The term “optionally substituted” in connection with these L groupsrefers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. Examples of L includethe groups L-1 through L-17 illustrated in Exhibit 3. In L-17, t is aninteger from 1 to 3. Although R⁶ groups are shown in the structure L-17,it is noted that they do not need to be present since they are optionalsubstituents. Preferred L groups are L-1, L-6, L-7, L-9 and L-10.

As noted above, R³ can be (among others) C₁-C₆ alkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, each optionally substituted with one tofive substituents independently selected from the group consisting of aphenyl ring and 5- or 6-membered heteroaromatic ring, each ringoptionally substituted with one to three substituents independentlyselected from R⁶. Examples of such rings incorporated into said R³groups include the rings illustrated as U-1 through U-53 and U-86illustrated in Exhibit 1, except that such rings are optionallysubstituted with 1 to 3 substituents independently selected from R⁶rather than (R^(v))_(r) and are attached to an R³ group selected fromthe list immediately above.

As noted above, R³ can be (among others) G; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, each optionally substitutedwith G; wherein G is a 5- or 6-membered nonaromatic carbocyclic orheterocyclic ring, optionally including one or two ring members selectedfrom the group consisting of C(═O), SO or S(O)₂ and optionallysubstituted with 1 to 4 substituents independently selected from R¹².The term “optionally substituted” in connection with these G groupsrefers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. The optionalsubstituents can be attached to any available carbon by replacing ahydrogen atom. Examples of 5- or 6-membered nonaromatic carbocyclicrings as G include the rings illustrated as G-1 through G-8 of Exhibit3. Examples of 5- or 6-membered nonaromatic heterocyclic rings as Ginclude the rings illustrated as G-9 through G-38 of Exhibit 4. Notethat when G comprises a ring selected from G-31 through G-34, G-37 andG-38, Q¹ is selected from O, S or N. Note that when G is G-11, G13,G-14, G16, G-23, G-24, G-30 through G-34, G-37 and G-38 and Q¹ is N, thenitrogen atom can complete its valence by substitution with either H orC₁-C₂ alkyl. Note that when the attachment point on the G group isillustrated as floating, the G group can be attached to the remainder ofFormula I through any available carbon of the G group by replacement ofa hydrogen atom.

As noted above, each R⁴ can be independently (among others) a phenyl,benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ringoptionally substituted with one to three substituents independentlyselected from R⁶. Examples of such R⁴ groups include the rings or ringsystems illustrated as U-1 through U-53, U-86 and U-87 illustrated inExhibit 1, except that such rings are optionally substituted with 1 to 3substituents independently selected from R⁶ rather than (R^(v))_(r).

As noted above, each R⁵ can be independently (among others) a phenyl,benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or anaromatic 8-, 9- or 10-membered fused heterobicyclic ring system, eachring optionally substituted with one to three substituents independentlyselected from R⁶. Examples of such R⁵ groups include the rings or ringsystems illustrated as U-1 through U-88 illustrated in Exhibit 1, exceptthat such rings are optionally substituted with 1 to 3 substituentsindependently selected from R⁶ rather than (R^(v))_(r).

Preferred compounds for reasons of better activity and/or ease ofsynthesis are:

-   -   Preferred 1. Compounds of Formula I above, their N-oxides and        agriculturally suitable salts thereof, wherein A and B are both        O and J is a phenyl group optionally substituted with 1 to 4 R⁵.    -   Preferred 2. Compounds of Preferred 1 wherein        -   one R⁴ group is attached to the K ring at either the            2-position or the 5-position, and said R⁴ is C₁-C₄ alkyl,            C₁-C₄ haloalkyl, halogen, CN, NO₂, C₁-C₄ alkoxy, C₁-C₄            haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄            alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl            or C₁-C₄ haloalkylsulfonyl; and        -   each R⁵ is independently halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy,            C₁-C₄ haloalkyl, CN, NO₂, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio,            C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄            haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄            haloalkylsulfonyl or C₂-C₄ alkoxycarbonyl; or        -   each R⁵ is independently a phenyl or a 5- or 6-membered            heteroaromatic ring, each ring optionally substituted with            one to three substituents independently selected from R⁶; or        -   two R⁵ groups when attached to adjacent carbon atoms are            taken together as —OCF₂O—, —CF₂CF₂O— or —OCF₂CF₂O—.    -   Preferred 3. Compounds of Preferred 2 wherein        -   R³ is C₁-C₄ alkyl optionally substituted with 1 to 5            substituents independently selected from the group            consisting of halogen, CN, OCH₃ and S(O)_(p)CH₃;        -   one R⁴ group is attached to the K ring at the 2-position and            said R⁴ is CH₃, CF₃, OCF₃, OCHF₂, S(O)_(p)CF₃, S(O)_(p)CHF₂,            CN or halogen;        -   an optionally second R⁴ is F, Cl, Br, I, CN or CF₃;        -   each R⁵ is independently halogen, methyl, CF₃, OCF₃, OCHF₂,            S(O)_(p)CF₃, S(O)_(p)CHF₂, OCH₂CF₃, OCF₂CHF₂, S(O)_(p)CH₂CF₃            or S(O)_(p)CF₂CHF₂; or a phenyl, pyrazole, imidazole,            triazole, pyridine or pyrimidine ring, each ring optionally            substituted with 1 to 3 substituents independently selected            from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen and CN; and        -   p is 0, 1 or 2.    -   Preferred 4. Compounds of Preferred 3 wherein R³ is C₁-C₄ alkyl.    -   Preferred 5. Compounds of Formula I above, their N-oxides and        agriculturally suitable salts thereof, wherein        -   A and B are both O;        -   J is a 5- or 6-membered heteroaromatic ring selected from            the group consisting of J-1, J-2, J-3, J-4 and J-5, each J            optionally substituted with 1 to 3 substituents            independently selected from R⁵

-   -   -   Q is O, S, NH or NR⁵; and        -   W, X, Y and Z are independently N, CH or CR⁵, provided that            in J-4 and J-5 at least one of W, X, Y or Z is N.

    -   Preferred 6. Compounds of Preferred 5 wherein        -   one R⁴ group is attached to the K ring at either the            2-position or the 5-position, and said R⁴ is C₁-C₄ alkyl,            C₁-C₄ haloalkyl, halogen, CN, NO₂, C₁-C₄ alkoxy, C₁-C₄            haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄            alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl,            or C₁-C₄ haloalkylsulfonyl; and        -   each R⁵ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl,            halogen, CN, NO₂, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄            alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio,            C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl or C₂-C₄            alkoxycarbonyl; or        -   each R⁵ is independently a phenyl or a 5- or 6-membered            heteroaromatic ring, each ring optionally substituted with            one to three substituents independently selected from R⁶.

    -   Preferred 7. Compounds of Preferred 6 wherein        -   J is selected from the group consisting of

-   -   -   R⁵ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, or

-   -   -   V is N, CH, CF, CCl, CBr or CI;        -   R⁶ is C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,            halogen, CN, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy or C₁-C₄            haloalkylthio;        -   R⁷ is H, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,            halogen, CN, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy or C₁-C₄            haloalkylthio;        -   R⁹ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆            haloalkenyl, C₃-C₆ alkynyl or C₃-C₆ haloalkynyl; provided R⁷            and R⁹ are not both H; and        -   m is 0 or 1.

    -   Preferred 8. Compounds of Preferred 7 wherein V is N.

    -   Preferred 9. Compounds of Preferred 7 wherein V is CH, CF, CCl        or CBr.

    -   Preferred 10. Compounds of Preferred 8 or Preferred 9 wherein        -   R³ is H; or C₁-C₄ alkyl optionally substituted with 1 to 5            substituents independently selected from the group            consisting of halogen, CN, OCH₃ and S(O)_(p)CH₃;        -   one R⁴ group is attached to the K ring at the 2-position and            said R⁴ is CH₃, CF₃, OCF₃, OCHF₂, S(O)_(p)CF₃, S(O)_(p)CHF₂,            CN or halogen;        -   an optionally second R⁴ is F, Cl, Br, I, CN or CF₃;        -   R⁶ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen or CN;        -   R⁷ is H, CH₃, CF₃, OCHF₂, OCH₂CF₃ or halogen; and        -   p is 0, 1 or 2.

    -   Preferred 11. Compounds of Preferred 10 wherein R³ is H or C₁-C₄        alkyl; and one R⁴ group is attached to the 2-position and said        R⁴ is CH₃, Cl, Br or I.

    -   Preferred 12. Compounds of Preferred 11 wherein J is J-6; R⁶ is        halogen; and R⁷ is halogen or CF₃.

    -   Preferred 13. Compounds of Preferred 12 wherein V is N; R³ is H        or methyl, ethyl, isopropyl or tertiary butyl; and R⁷ is Br, Cl        or CF₃.

    -   Preferred 14. Compounds of Preferred 11 wherein J is J-7; R⁶ is        halogen; and R⁹ is CF₃, CHF₂, CH₂CF₃ or CF₂CHF₂.

    -   Preferred 15. Compounds of Preferred 11 wherein J is J-8; R⁶ is        halogen; and R⁷ is halogen or CF₃.

    -   Preferred 16. Compounds of Preferred 11 wherein J is J-9; R⁶ is        halogen; and R⁷ is CF₃.

    -   Preferred 17. Compounds of Preferred 11 wherein J is J-10; R⁶ is        halogen; and R⁹ is CF₃, CHF₂, CH₂CF₃ or CF₂CHF₂.

    -   Preferred 18. Compounds of Preferred 11 wherein J is J-11; R⁶ is        halogen; and R⁷ is halogen or CF₃.

    -   Preferred 19. Compounds of Preferred 11 wherein J is J-12; R⁶ is        halogen; R⁷ is H, halogen or CF₃; and R⁹ is H, CF₃, CHF₂,        CH₂CF₃, or CF₂CHF₂.

    -   Preferred 20. Compounds of Preferred 11 wherein J is J-13; R⁶ is        halogen; R⁷ is H, halogen or CF₃; and R⁹ is H, CF₃, CHF₂, CH₂CF₃        or CF₂CHF₂.

Most preferred are compounds of Preferred 13 selected from the group:

-   -   6-Bromo-1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-8-methyl-3-(1-methylethyl)-2,4(1H,3H)-quinazolinedione,    -   6-Bromo-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-3,8-dimethyl-2,4(1H,3H)-quinazolinedione,    -   6-Bromo-1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-3,8-dimethyl-2,4(1H,3H)-quinazolinedione,    -   1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone,    -   6,8-Dichloro-1-[[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3-(1-methylethyl)-4(1H)-quinazolinone,    -   1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-6,8-dichloro-2,3-dihydro-3-(1-methylethyl)-4-(1H)-quinazolinone,    -   6,8-Dichloro-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3-methyl-4(1H)-quinazolinone,    -   6-Chloro-1-[[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone,    -   1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-6-chloro-2,3-dihydro-8-methyl-3-(1-methylethyl)-4-(1H)-quinazolinone,    -   6,8-Dichloro-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3-(1-methylethyl)-4(1H)-quinazolinone,    -   6-8-Dichloro-1-[[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3-methyl-4(1H)-quinazolinone,    -   1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-6,8-dichloro-2,3-dihydro-3-methyl-4(1H)-quinazolinone,    -   6-Chloro-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone,    -   6-Chloro-1-[[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3,8-dimethyl-4(1H)-quinazolinone,    -   1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-6-chloro-2,3-dihydro-3,8-dimethyl-4(1H)-quinazolinone,    -   6-Chloro-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-3,8-dimethyl-4(1H)-quinazolinone,    -   6,8-Dichloro-1-[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-4(1H)-quinazolinone        and    -   6,8-Dichloro-1-[[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-4(1H)-quinazolinone.

This invention also pertains to a composition for controlling aninvertebrate pest comprising a biologically effective amount of acompound of Formula I and at least one additional component selectedfrom the group consisting of surfactants, an N-oxide thereof or asuitable salt thereof solid diluents and liquid diluents. This inventionalso pertains to a composition comprising a biologically effectiveamount of a compound of Formula I and an effective amount of at leastone additional biologically active compound or agent. The preferredcompositions of the present invention are those which comprise the abovepreferred compounds.

This invention also pertains to a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of Formula I (e.g., as acomposition described herein). This invention also relates to such amethod wherein the invertebrate pest or its environment is contactedwith a biologically effective amount of a compound of Formula I or acomposition comprising a compound of Formula I and a biologicallyeffective amount of at least one additional compound or agent forcontrolling invertebrate pests. The preferred methods of use are thoseinvolving the above preferred compounds.

The compounds of Formula I can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-1. Thedefinitions of A, B, J, K, L, R³, R⁴, R⁵ and n in the compounds ofFormulae I and 2-23 below are as defined above in the Summary of theInvention. Compounds of Formulae Ia-Ic, If, 2a-c, 9a-i and 10a-c arevarious subsets of the compounds of Formula I, 2, 9 and 10, respectivelyand all substituents for Formulae Ia-If are as defined above for FormulaI.

As shown in Scheme 1, compounds of Formula I can be prepared by thereaction of aryl or heteroaryl amines of Formula 2 with acid chloridesof Formula 3 in the presence of a base to provide a compound of FormulaIa. The reaction can be run neat or in a variety of suitable solventsincluding tetrahydrofuran, toluene, methylene-chloride and chloroformwith optimum temperatures ranging from room temperature to the refluxtemperature of the solvent. Typical bases used in the reaction includeamines such as triethylamine and pyridine, carbonates such as potassiumand sodium carbonate and hydrides such as potassium and sodium hydride.In a subsequent step, compounds of Formula Ia can be converted tocompounds of Formula Ib using a variety of standard thio transferreagents including phosphorus pentasulfide and(2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide).

The preparation of compounds of Formula Ic, i.e. compounds of Formula Iwherein K is K-1, is outlined in Scheme 2. Reaction of aquinazolinedione of Formula 2a (wherein L is CO) or a derivative ofFormula 2b (wherein L is C₁-C₃ alkyl optionally substituted with one tothree substituents independently selected from R¹³), with an acidchloride of Formula 3 provides a compound of Formula Ic. Theseprocedures can also be applied to prepare compounds of Formula I whereinK is selected from K-2 through K-6.

As shown in Scheme 3, compounds Formula 2a can be prepared in two stepsfrom known isatoic anhydrides. In the first step an isatoic anhydride ofFormula 4 is reacted directly with an amine of Formula 5 either neat orin a suitable solvent to afford an amide of Formula 6. Treatment of theamide of Formula 6 with phosgene or a phosgene equivalent affords thequinazolinedione of Formula 2a.

As shown in Scheme 4, compounds of Formula 2b, wherein Rx and Ry areindependently H and subsets of R¹³, can be prepared from compounds ofFormula 6 by reaction with an aldehyde or ketone generally in thepresence of an acid catalyst such as p-toluenesulfonic acid (pTSA).Azeotropic removal of the water as it is formed, or other methods ofdrying, can be useful in driving the reaction to completion.

As shown in Scheme 5, compounds of Formula 2c can be prepared by theSchmidt reaction from tetrahydroquinolinones of Formula 8 and sodiumazide (J. Het. Chem. 1971, 8, 231-236). Reaction of a compound ofFormula 2c with an acid chloride 3 in the presence of a base such astriethylamine affords a product of Formula If.

Acid chlorides of Formula 3 are well documented in the chemicalliterature and generally derived from the corresponding known aryl andheteroaryl carboxylic acids of Formula 9. Many of the carboxylic acidsof Formula 9 are known in the literature. Procedures for the preparationof specific preferred acids of Formula 9a-9f and their derived acidchlorides are described in WO 01/70671.

The pyridylpyrazole carboxylic acids of Formula 9g-9i are a specificallypreferred set of acids of Formula 9 (Scheme 7). Reaction of a pyrazoleof Formula 10 with 2,3-dichloropyridine of Formula 11 affords goodyields of the 1-pyridylpyrazole of Formula 12 with good specificity forthe desired regiochemistry. Metallation of compounds of Formula 12 withlithium diisopropylamide (LDA) followed by quenching of the lithium saltwith carbon dioxide affords the pyrazole acids of Formula 9g-9i.Additional details for the synthesis of Formula 9i are provided inExample 1.

The starting pyrazoles of Formula 10 are known compounds or can beprepared according to known methods. Pyrazole 10a can be prepared byliterature procedures (J. Fluorine Chem. 1991, 53(1), 61-70). Pyrazolesof Formulae 10b and 10c can also be prepared by literature procedures(Chem. Ber. 1966, 99(10), 3350-7). A useful alternative for thepreparation of 10b and 10c is depicted in Scheme 8. Metallation of thesulfamoyl pyrazole of Formula 13 with n-butyllithium (n-BuLi) followedby direct halogenation of the anion with either hexachloroethane or1,2-dibromotetrachloroethane affords the halogenated derivatives ofFormula 14. Removal of the sulfamoyl group with trifluoroacetic acid(TFA) at room temperature proceeds cleanly and in good yield to affordthe pyrazoles 10b and 10c respectively. Further experimental details forthese procedures are described in Example 1.

As an alternative to the method illustrated in Scheme 7,pyrazolecarboxylic acids of Formula 9h and 9i can be prepared by themethod outlined in Scheme 9. Reaction of hydrazinopyridine 15 withdiethyl maleate affords pyrazolone 16. Chlorination or bromination withphosphorus oxychloride or phosphorus oxybromide affords the haloderivatives of Formula 17. Oxidization of a compound of Formula 17optionally in the presence of acid to give a pyrazole ester followed byconversion of the ester function to the carboxylic acid provides acompound of Formula 9h or 9i. The oxidizing agent can be hydrogenperoxide, organic peroxides, potassium persulfate, sodium persulfate,ammonium persulfate, potassium monopersulfate (e.g., Oxone®) orpotassium permanganate.

As an alternative to the method illustrated in Scheme 7,pyrazolecarboxylic acids of Formula 9g wherein R⁵ is CF₃ can also beprepared by the method outlined in Scheme 10.

Reaction of a compound of Formula 18 with a suitable base in a suitableorganic solvent affords the cyclized product of Formula 19 afterneutralization with an acid such as acetic acid. The suitable base canbe, for example, sodium hydride, potassium t-butoxide, dimsyl sodium(CH₃S(O)CH₂ ^({circle around (−)})Na^({circle around (+)})), alkalimetal (such as lithium, sodium or potassium) carbonates or hydroxides,tetraalkyl (such as methyl, ethyl or butyl)ammonium fluorides orhydroxides, or2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphonine.The suitable organic solvent can be, for example, acetone, acetonitrile,tetrahydrofuran, dichloromethane, dimethylsulfoxide, orN,N-dimethylformamide. Dehydration of the compound of Formula 19 to givethe compound of Formula 20, followed by converting the carboxylic esterfunction to carboxylic acid, affords the acids of Formula 9g. Thedehydration is effected by treatment with a catalytic amount of asuitable acid such as sulfuric acid.

Compounds of Formula 18 can be prepared by the method outlined in Scheme11.

wherein R⁵ is CF₃.

Treatment of a hydrazine compound of Formula 21 with a ketone of Formula22 in a solvent such as water, methanol or acetic acid gives thehydrazone of Formula 23. Reaction of the hydrazone of Formula 23 withethyl oxalyl chloride in a suitable organic solvent such asdichloromethane or tetrahydrofuran in the presence of an acid scavengersuch as triethylamine provides the compound of Formula 18. Hydrazinecompounds of Formula 21 can be prepared by standard methods, such as bycontacting the corresponding halo compound of Formula 11 with hydrazine.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula I may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula I. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula I. One skilled in the art will also recognize that compounds ofFormula I and the intermediates described herein can be subjected tovarious electrophilic, nucleophilic, radical, organometallic, oxidation,and reduction reactions to add substituents or modify existingsubstituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except for chromatographic solventmixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; s is singlet, d is doublet, t is triplet, q isquartet, m is multiplet, dd is doublet of doublets, dt is doublet oftriplets, br s is broad singlet.

EXAMPLE 16-Bromo-1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-8-methyl-3-(1-methylethyl)-2,4(1H,3H)-quinazolinedione

Step A: Preparation of 3-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide

To a solution of N-dimethylsulfamoylpyrazole (44.0 g, 0.251 mol) in drytetrahydrofuran (500 mL) at −78° C. was added dropwise a solution ofn-butyllithium (2.5 M in hexane, 105.5 mL, 0.264 mol) while maintainingthe temperature below −60° C. A thick solid formed during the addition.Upon completion of the addition the reaction mixture was maintained foran additional 15 minutes, after which time a solution of1,2-dibromo-tetrachloroethane (90 g, 0.276 mol) in tetrahydrofuran (150mL) was added dropwise while maintaining the temperature below −70° C.The reaction mixture turned a clear orange; stirring was continued foran additional 15 minutes. The −78° C. bath was removed and the reactionwas quenched with water (600 mL). The reaction mixture was extractedwith dichloromethane (4×), and the organic extracts were dried overmagnesium sulfate and concentrated. The crude product was furtherpurified by chromatography on silica gel using dichloromethane/hexane(50:50) as eluent to afford the title product as a clear colorless oil(57.04 g).

¹H NMR (CDCl₃) δ 3.07 (d,6H), 6.44 (m, 1H), 7.62 (m, 1H).

Step B: Preparation of 3-bromopyrazole

To trifluoroacetic acid (70 mL) was slowly added the bromopyrazoleproduct (57.04 g) from Step A. The reaction mixture was stirred at roomtemperature for 30 minutes and then concentrated at reduced pressure.The residue was taken up in hexane, insoluble solids were filtered off,and the hexane was evaporated to afford the crude product as an oil. Thecrude product was further purified by chromatography on silica gel usingethyl acetate/dichloromethane (10:90) as eluent to afford an oil. Theoil was taken up in dichloromethane, neutralized with aqueous sodiumbicarbonate solution, extracted with dichloromethane (3×), dried overmagnesium sulfate and concentrated to afford the title product as awhite solid (25.9 g), m.p. 61-64° C.

¹H NMR (CDCl₃) δ 6.37 (d,1H), 7.59 (d,1H), 12.4 (br s,1H).

Step C: Preparation of 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine

To a mixture of 2,3-dichloropyridine (27.4 g, 185 mmol) and3-bromopyrazole (25.4 g, 176 mmol) in dry N,N-dimethylformamide (88 mL)was added potassium carbonate (48.6 g, 352 mmol), and the reactionmixture was heated to 125° C. for 18 hours. The reaction mixture wascooled to room temperature and poured into ice water (800 mL). Aprecipitate formed. The precipitated solids were stirred for 1.5 hrs,filtered and washed with water (2×100 mL). The solid filter cake wastaken up in dichloromethane and washed sequentially with water, 1Nhydrochloric acid, saturated aqueous sodium bicarbonate solution, andbrine. The organic extracts were then dried over magnesium sulfate andconcentrated to afford 39.9 g of a pink solid. The crude solid wassuspended in hexane and stirred vigorously for 1 hour. The solids werefiltered, washed with hexane and dried to afford the title product as anoff-white powder (30.4 g) determined to be >94% pure by NMR. Thismaterial was used without further purification in Step D.

1H NMR (CDCl₃)H), δ 6.52 (s,1H), 7.30 (dd,1H), 8.05 (s,1H), 8.43 (d,1H).

Step D: Preparation of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid

To a solution of the pyrazole product from Step C (30.4 g, 118 mmol) indry tetrahydrofuran (250 mL) at −76° C. was added dropwise a solution oflithium diisopropylamide (118 mmol) in tetrahydrofuran at such a rate asto maintain the temperature below −71° C. The reaction mixture wasstirred for 15 minutes at −76° C., and carbon dioxide was then bubbledthrough for 10 minutes, causing warming to −57° C. The reaction mixturewas warmed to −20° C. and quenched with water. The reaction mixture wasconcentrated and then taken up in water (1 L) and ether (500 mL), andthen aqueous sodium hydroxide solution (1 N, 20 mL) was added. Theaqueous extracts were washed with ether and acidified with hydrochloricacid. The precipitated solids were filtered, washed with water and driedto afford the title product as a tan solid (27.7 g). (Product fromanother run following similar procedure melted at 200-201° C.)

¹H NMR (DMSO-d₆) δ 7.25 (s, 1H), 7.68 (dd, 1H), 8.24 (d, 1H), 8.56 (d,1H).

Step E: Preparation of 6-bromo-8-methyl-2H-3,1-benzoxazine-2,4(1H)-dione

To a solution of 8-methyl-2H-3,1-benzoxazine-2,4(1H)-dione, (10.0 g,56.5 mmol) and potassium iodide (0.36 g, 1.8 mmol) in chlorosulfonicacid (12 mL) was added bromine (4.6 g, 28.7 mmol). and the reaction wasstirred overnight at room temperature. The reaction was then slowlypoured onto ice water and neutralized with sodium bicarbonate powder toa pH of 7. The solids were filtered, rinsed with water and to afford thedesired intermediate as a white solid (11.4 g).

¹H NMR (DMSO) δ 2.34 (s,3H), 7.76 (m,3H), 7.85 (m,1H), 11.21 (s,1H).

Step F: Preparation of2-amino-5-bromo-3-methyl-N-(1-methylethyl)benzamide

To a suspension of the benzoxazinedione of Step E, (4.0 g, 15.56 mmol)in pyridine (20 mL) was added isopropylamine (1.2 g, 20.23 mmol) and thereaction was heated to reflux for 2 hours. The reaction was then cooled,concentrated from toluene on a rotary evaporator and then dried undervacuum to afford a solid (5.01 g).

¹H NMR (DMSO) δ 1.29 (d,6H), 2.15 (s,3H), 4.25 (m,1H), 5.75 (m,1H), 7.24(m,1H) 7.27 (m,1H).

Step G: Preparation of6-bromo-8-methyl-3-(1-methylethyl)-2,4(1H,3H)-quinazolinedione

To a solution of the anthranilamide of Step F, (1.11 g, 4.1 mmol) indioxane (20 mL) was added a 2.0 M solution of phosgene in toluene (2.3mL, 4.6 mmol). The reaction was stirred at room temperature for 1 hourthen heated to reflux for 4 hours and cooled to room temperature. Thewhite solids were filtered and dried to afford the title compound (0.89g).

¹H NMR (DMSO) δ 1.43 (d,6H), 2.34 (s,3H), 5.12 (m,1H), 7.67 (s,1H), 7.85(s,1H).

Step H: Preparation of6-bromo-1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-8-methyl-3-(1-methylethyl)-2,4(1H,3H)-quinazolinedione

To a solution of the quinazolinedione of Step G (245 mg, 0.825 mmol) indimethylformamide (5 mL) was added sodium hydride (60% oil dispersion,36 mg, 0.90 mmol) and the reaction was allowed to stir at roomtemperature. In a separate reaction flask containing a solution of thepyrazole acid of Step D (500 mg, 1.65 mmol) in dichloromethane (10 mL)was added oxalyl chloride (0.17 mL, 1.95 mmol) and one drop of DMF. Thismixture was stirred for 2 hours, then concentrated and placed undervacuum. The acid chloride was divided into two equal portions. One ofthese portions was taken up in 5 mL of DMF and added to thequinazolinedione/NaH reaction mixture and the resulting mixture wasstirred at room temperature for 3 hours. The reaction was partitionedbetween ethyl acetate and water, washed twice with water, then withbrine and dried over sodium sulfate. The crude product was purified bychromatography on silica gel with 99:1 chloroform/acetone as eluent toafford the title compound, a compound of the present invention.

¹H NMR (CDCl₃) δ 1.47 (d,6H), 2.17 (s,3H), 5.08 (m,1H), 7.12 (s,1H),7.39 (dd,1H), 7.54 (d,1H), 7.91 (dd,1H), 8.17 (d,1H), 8.34 (dd,1H).

EXAMPLE 2 Preparation of1-[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone

Step A: Preparation of2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone

To a solution of 2-amino-3-methyl-N-(1-methylethyl)benzamide (0.5 g, 2.6mmol) in ethanol (10 mL) was added paraformaldehyde (78 mg, 2.6 mmol)and p-toluenesulfonic acid (18 mg, 95 μmol) and the mixture was heatedat reflux until it became clear (approximately 4 hours). The solvent wasremoved under reduced pressure to give the title compound (95% pure)which was used without further purification.

¹H NMR (CDCl₃) δ 7.9-7.8 (d,1H), 7.2-7.1 (d,1H), 6.83 (t,1H), 4.97(m,1H), 4.57 (s,2H), 2.17 (s,3H), 1.22 (d,6H).

Step B: Preparation of1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone

To a solution of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (787 mg,2.45 mmol) (i.e. the product of Example 1, Step D) in dichloromethane(10 mL) was added dimethylformamide (20 μL) and oxalyl chloride (235μL). The mixture was stirred for 1 hour, at which point it had becomeclear. After removing volatiles under reduced pressure, the residue wasdissolved in dichloromethane (5 mL) and one half of the solution wasadded to a mixture of the product of Step A (0.25 g, 1.2 mmol) andpyridine (148 μL, 1.8 mmol) in methylene chloride (10 mL). Afterstirring at ambient temperature overnight,1,5,7-triazabicyclo[4.4.0]dec-5-ene bound to polystyrene crosslinkedwith 2% DVB (1 g) (Fluka Chemie AG catalog number 90603) was added andthe mixture was stirred for an additional 15 minutes. The mixture wasthen filtered and concentrated under reduced pressure. The resultingresidue was purified by chromatography on silica gel to give the titlecompound, a compound of the invention, as a white solid (0.18 g).

¹H NMR (CDCl₃) δ 8.3 (m,1H), 7.9-7.8 (m,2H), 7.4-7.3 (m,3H), 6.0-5.9(s,1H), 5.9 (d,1H), 5.0-4.8 (m,1H), 4.4-4.3 (d,1H), 2.10 (s,3H), 1.3-1.1(m,6H).

The following Example 3 illustrates an alternative preparation of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid, whichcan be used to prepare, for example,6-bromo-1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-8-methyl-3-(1-methylethyl)-2,4(1H,3H)-quinazolinedioneand1-[[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]-2,3-dihydro-8-methyl-3-(1-methylethyl)-4(1H)-quinazolinone,by further steps illustrated in Example 1 and 2.

EXAMPLE 3 Preparation of3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid

Step A: Preparation of Ethyl2-(3-Chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate

A 2-L four-necked flask equipped with a mechanical stirrer, thermometer,addition funnel, reflux condenser, and nitrogen inlet was charged withabsolute ethanol (250 mL) and an ethanolic solution of sodium ethoxide(21%, 190 mL, 0.504 mol). The mixture was heated to reflux at about 83°C. It was then treated with 3-chloro-2(1H)-pyridinone hydrazone (68.0 g,0.474 mol). The mixture was re-heated to reflux over a period of 5minutes. The yellow slurry was then treated dropwise with diethylmaleate (88.0 mL, 0.544 mol) over a period of 5 minutes. The reflux rateincreased markedly during the addition. By the end of the addition allof the starting material had dissolved. The resulting orange-redsolution was held at reflux for 10 minutes. After being cooled to 65°C., the reaction mixture was treated with glacial acetic acid (50.0 mL,0.873 mol). A precipitate formed. The mixture was diluted with water(650 mL), causing the precipitate to dissolve. The orange solution wascooled in an ice bath. Product began to precipitate at 28° C. The slurrywas held at about 2° C. for 2 hours. The product was isolated viafiltration, washed with aqueous ethanol (40%, 3×50 mL), and thenair-dried on the filter for about 1 hour. The title product compound wasobtained as a highly crystalline, light orange powder (70.3 g, 55%yield). No significant impurities were observed by ¹H NMR.

¹H NMR (DMSO-d₆) δ 1.22 (t, 3H), 2.35 (d, 1H), 2.91 (dd, 1H), 4.20 (q,2H), 4.84 (d, 1H), 7.20 (dd, 1H), 7.92 (d, 1H), 8.27 (d, 1H), 10.18 (s,1H).

Step B: Preparation of Ethyl3-Bromo-1-(3-chloro-2-pyridinyl)-4,5-dihydro-1H-pyrazole-5-carboxylate

A 1-L four-necked flask equipped with a mechanical stirrer, thermometer,reflux condenser, and nitrogen inlet was charged with acetonitrile (400mL), ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate(i.e. the product of Step A) (50.0 g, 0.185 mol) and phosphorusoxybromide (34.0 g, 0.119 mol). The orange slurry was heated to refluxat 83° C. over a period of 20 minutes. The resulting turbid, orangesolution was held at reflux for 75 minutes, at which time a dense, tan,crystalline precipitate had formed. The reflux condenser was replacedwith a distillation head, and a cloudy, colorless distillate (300 mL)was collected. A second 1-L four-necked flask equipped with a mechanicalstirrer was charged with sodium bicarbonate (45 g, 0.54 mol) and water(200 mL). The concentrated reaction mixture was added to the sodiumbicarbonate slurry over a period of 5 minutes. The resulting two-phasemixture was stirred vigorously for 5 minutes, at which time gasevolution had ceased. The mixture was diluted with dichloromethane (200mL) and then was stirred for 75 minutes. The mixture was treated with 5g of Celite® 545 diatomaceous filter aid and then filtered to remove abrown, tarry substance. The filtrate was transferred to a separatoryfunnel. The brown organic layer (400 mL) was separated and then wastreated with magnesium sulfate (15 g) and Darco® G60 activated charcoal(2.0 g). The resulting slurry was stirred magnetically for 15 minutesand then filtered to remove the magnesium sulfate and charcoal. Thegreen filtrate was treated with silica gel (3 g) and stirred for severalminutes. The deep blue-green silica gel was removed by filtration, andthe filtrate was concentrated on a rotary evaporator. The productconsisted of a light amber oil (58.6 g, 95% yield), which crystallizedupon standing. The only appreciable impurity observed by ¹H NMR was 0.3%acetonitrile.

¹H NMR (DMSO-d₆) δ 1.15 (t, 3H), 3.29 (dd, 1H), 3.60 (dd, 1H), 4.11 (q,2H), 5.20 (dd, 1H), 6.99 (dd, 1H), 7.84 (d, 1H), 8.12 (d, 1H).

Step C: Preparation of Ethyl3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylate

A 1-L four-necked flask equipped with a mechanical stirrer, thermometer,reflux condenser, and nitrogen inlet was charged with ethyl3-bromo-1-(3-chloro-2-pyridinyl)-4,5-dihydro-1H-pyrazole-5-carboxylate(i.e. the product of Step B) (40.2 g, 0.121 mol), acetonitrile (300 mL)and sulfuric acid (98%, 13.0 mL, 0.245 mol). The mixture self-heatedfrom 22 to 36° C. upon adding the sulfuric acid. After being stirred forseveral minutes, the mixture was treated with potassium persulfate (48.0g, 0.178 mol). The slurry was heated to reflux at 84° C. for 2 hours.The resulting orange slurry while still warm (50-65° C.) was filtered toremove a white precipitate. The filter cake was washed with acetonitrile(2×50 mL). The filtrate was concentrated to about 200 mL on a rotaryevaporator. A second 1-L four-necked flask equipped with a mechanicalstirrer was charged with water (400 mL). The concentrated reaction masswas added to the water over a period of about 5 minutes. The product wasisolated via filtration, washed sequentially with aqueous acetonitrile(20%, 100 mL) and water (75 mL), and was then air-dried on the filterfor 1 hour. The product consisted of a crystalline, orange powder (36.6g, 90% yield). The only appreciable impurities observed by ¹H NMR wereabout 1% of an unknown and 0.5% acetonitrile.

¹H NMR (DMSO-d₆) δ 1.09 (t, 3H), 4.16 (q, 2H), 7.35 (s, 1H), 7.72 (dd,1H), 8.39 (d, 1H), 8.59 (d, 1H).

Step D: Preparation of3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid

A 300-mL four-necked flask equipped with a mechanical stirrer,thermometer, and nitrogen inlet was charged with ethyl3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylate (i.e. theproduct of Step C) (98.5% pure, 25.0 g, 0.0756 mol), methanol (75 mL),water (50 mL), and sodium hydroxide pellets (3.30 g, 0.0825 mol). Uponadding the sodium hydroxide the mixture self-heated from 29 to 34° C.and the starting material began to dissolve. After being stirred for 90minutes under ambient conditions, all of the starting material haddissolved. The resulting dark orange solution was concentrated to about90 mL on a rotary evaporator. The concentrated reaction mixture was thendiluted with water (160 mL). The aqueous solution was extracted withether (100 mL). Then the aqueous layer was transferred to a 500-mLErlenmeyer flask equipped with a magnetic stirrer. The solution wastreated dropwise with concentrated hydrochloric acid (8.50 g, 0.0839mol) over a period of about 10 minutes. The product was isolated viafiltration, reslurried with water (2×40 mL), cover washed once withwater (25 mL), and then air-dried on the filter for 2 hours. The productconsisted of a crystalline, tan powder (20.9 g, 91% yield). The onlyappreciable impurities observed by ¹H NMR were about 0.8% of an unknownand 0.7% ether.

¹H NMR (DMSO-d₆) δ 7.25 (s, 1H), 13.95 (br s, 1H), 8.56 (d, 1H), 8.25(d, 1H), 7.68 (dd, 1H).

By the procedures described herein together with methods known in theart, the following compounds of Tables 1 to 10 can be prepared. Thefollowing abbreviations are used in the Tables which follow: t istertiary, s is secondary, n is normal, i is iso, c is cyclo, Me ismethyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl andt-Bu is tertiary butyl.

TABLE 1

R³ R^(4a) R^(4b) R^(5a) R^(5b) L is C═O H Me H Me CF₃ H Cl H Me CF₃ H MeCl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-Pr Me H Me CF₃i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr Me Br Me CF₃i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me Cl Me CF₃t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H Me CF₃ EtCl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et Cl Br MeCF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃ Me MeBr Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl Me OCF₃H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃ i-PrCl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br Me OCF₃i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me Cl MeOCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me H MeOCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br Me OCF₃Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃ Me ClCl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ H Cl HMe CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br Me CF(CF₃)₂H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂ i-Pr MeCl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂ i-Pr Cl BrMe CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-Bu Me Cl MeCF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu Cl Br MeCF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl Me CF(CF₃)₂ EtCl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂ Me Me H MeCF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl Me CF(CF₃)₂Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂ H Me H Me CF₃ H Cl HMe CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-PrMe H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr MeBr Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me ClMe CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H MeCF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et ClBr Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl MeOCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br MeOCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me ClMe OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me HMe OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br MeOCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ HCl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br MeCF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-BuMe Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu ClBr Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl MeCF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl MeCF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂CH₂ H Me H MeCF₃ H Cl H Me CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl BrMe CF₃ i-Pr Me H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl MeCF₃ i-Pr Me Br Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H MeCF₃ t-Bu Me Cl Me CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br MeCF₃ Et Me H Me CF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et MeBr Me CF₃ Et Cl Br Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃Me Cl Cl Me CF₃ Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H MeOCF₃ H Me Cl Me OCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃i-Pr Me H Me OCF₃ i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl MeOCF₃ i-Pr Me Br Me OCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl HMe OCF₃ t-Bu Me Cl Me OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu ClBr Me OCF₃ Et Me H Me OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl MeOCF₃ Et Me Br Me OCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃Me Me Cl Me OCF₃ Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H MeH Me CF(CF₃)₂ H Cl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂H Me Br Me CF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl HMe CF(CF₃)₂ i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br MeCF(CF₃)₂ i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H MeCF(CF₃)₂ t-Bu Me Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br MeCF(CF₃)₂ t-Bu Cl Br Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂Et Me Cl Me CF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl BrMe CF(CF₃)₂ Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂Me Cl Cl Me CF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂

TABLE 2

R³ R^(4a) R^(4b) R^(5a) R^(5b) L is C═O H Me H Me CF₃ H Cl H Me CF₃ H MeCl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-Pr Me H Me CF₃i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr Me Br Me CF₃i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me Cl Me CF₃t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H Me CF₃ EtCl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et Cl Br MeCF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃ Me MeBr Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl Me OCF₃H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃ i-PrCl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br Me OCF₃i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me Cl MeOCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me H MeOCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br Me OCF₃Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃ Me ClCl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ H Cl HMe CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br Me CF(CF₃)₂H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂ i-Pr MeCl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂ i-Pr Cl BrMe CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-Bu Me Cl MeCF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu Cl Br MeCF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl Me CF(CF₃)₂ EtCl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂ Me Me H MeCF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl Me CF(CF₃)₂Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂ H Me H Me CF₃ H Cl HMe CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-PrMe H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr MeBr Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me ClMe CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H MeCF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et ClBr Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl MeOCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br MeOCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me ClMe OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me HMe OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br MeOCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ HCl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br MeCF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-BuMe Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu ClBr Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl MeCF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl MeCF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂CH₂ H Me H MeCF₃ H Cl H Me CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl BrMe CF₃ i-Pr Me H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl MeCF₃ i-Pr Me Br Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H MeCF₃ t-Bu Me Cl Me CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br MeCF₃ Et Me H Me CF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et MeBr Me CF₃ Et Cl Br Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃Me Cl Cl Me CF₃ Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H MeOCF₃ H Me Cl Me OCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃i-Pr Me H Me OCF₃ i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl MeOCF₃ i-Pr Me Br Me OCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl HMe OCF₃ t-Bu Me Cl Me OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu ClBr Me OCF₃ Et Me H Me OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl MeOCF₃ Et Me Br Me OCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃Me Me Cl Me OCF₃ Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H MeH Me CF(CF₃)₂ H Cl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂H Me Br Me CF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl HMe CF(CF₃)₂ i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br MeCF(CF₃)₂ i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H MeCF(CF₃)₂ t-Bu Me Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br MeCF(CF₃)₂ t-Bu Cl Br Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂Et Me Cl Me CF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl BrMe CF(CF₃)₂ Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂Me Cl Cl Me CF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂

TABLE 3

R³ R^(4a) R^(4b) R^(5a) R^(5b) L is C═O H Me H Me CF₃ H Cl H Me CF₃ H MeCl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-Pr Me H Me CF₃i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr Me Br Me CF₃i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me Cl Me CF₃t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H Me CF₃ EtCl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et Cl Br MeCF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃ Me MeBr Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl Me OCF₃H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃ i-PrCl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br Me OCF₃i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me Cl MeOCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me H MeOCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br Me OCF₃Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃ Me ClCl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ H Cl HMe CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br Me CF(CF₃)₂H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂ i-Pr MeCl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂ i-Pr Cl BrMe CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-Bu Me Cl MeCF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu Cl Br MeCF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl Me CF(CF₃)₂ EtCl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂ Me Me H MeCF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl Me CF(CF₃)₂Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂ H Me H Me CF₃ H Cl HMe CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-PrMe H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr MeBr Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me ClMe CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H MeCF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et ClBr Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl MeOCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br MeOCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me ClMe OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me HMe OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br MeOCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ HCl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br MeCF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-BuMe Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu ClBr Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl MeCF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl MeCF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂CH₂ H Me H MeCF₃ H Cl H Me CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl BrMe CF₃ i-Pr Me H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl MeCF₃ i-Pr Me Br Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H MeCF₃ t-Bu Me Cl Me CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br MeCF₃ Et Me H Me CF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et MeBr Me CF₃ Et Cl Br Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃Me Cl Cl Me CF₃ Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H MeOCF₃ H Me Cl Me OCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃i-Pr Me H Me OCF₃ i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl MeOCF₃ i-Pr Me Br Me OCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl HMe OCF₃ t-Bu Me Cl Me OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu ClBr Me OCF₃ Et Me H Me OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl MeOCF₃ Et Me Br Me OCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃Me Me Cl Me OCF₃ Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H MeH Me CF(CF₃)₂ H Cl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂H Me Br Me CF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl HMe CF(CF₃)₂ i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br MeCF(CF₃)₂ i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H MeCF(CF₃)₂ t-Bu Me Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br MeCF(CF₃)₂ t-Bu Cl Br Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂Et Me Cl Me CF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl BrMe CF(CF₃)₂ Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂Me Cl Cl Me CF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂

TABLE 4

R³ R^(4a) R^(4b) R^(5a) R^(5b) L is C═O H Me H Me CF₃ H Cl H Me CF₃ H MeCl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-Pr Me H Me CF₃i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr Me Br Me CF₃i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me Cl Me CF₃t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H Me CF₃ EtCl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et Cl Br MeCF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃ Me MeBr Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl Me OCF₃H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃ i-PrCl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br Me OCF₃i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me Cl MeOCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me H MeOCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br Me OCF₃Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃ Me ClCl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ H Cl HMe CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br Me CF(CF₃)₂H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂ i-Pr MeCl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂ i-Pr Cl BrMe CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-Bu Me Cl MeCF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu Cl Br MeCF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl Me CF(CF₃)₂ EtCl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂ Me Me H MeCF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl Me CF(CF₃)₂Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂ H Me H Me CF₃ H Cl HMe CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl Br Me CF₃ i-PrMe H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl Me CF₃ i-Pr MeBr Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H Me CF₃ t-Bu Me ClMe CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br Me CF₃ Et Me H MeCF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et Me Br Me CF₃ Et ClBr Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃ Me Cl Cl Me CF₃Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H Me OCF₃ H Me Cl MeOCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃ i-Pr Me H Me OCF₃i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl Me OCF₃ i-Pr Me Br MeOCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl H Me OCF₃ t-Bu Me ClMe OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu Cl Br Me OCF₃ Et Me HMe OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl Me OCF₃ Et Me Br MeOCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃ Me Me Cl Me OCF₃Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H Me H Me CF(CF₃)₂ HCl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂ H Me Br MeCF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl H Me CF(CF₃)₂i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br Me CF(CF₃)₂i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H Me CF(CF₃)₂ t-BuMe Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br Me CF(CF₃)₂ t-Bu ClBr Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂ Et Me Cl MeCF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl Br Me CF(CF₃)₂Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂ Me Cl Cl MeCF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂ L is CH₂CH₂ H Me H MeCF₃ H Cl H Me CF₃ H Me Cl Me CF₃ H Cl Cl Me CF₃ H Me Br Me CF₃ H Cl BrMe CF₃ i-Pr Me H Me CF₃ i-Pr Cl H Me CF₃ i-Pr Me Cl Me CF₃ i-Pr Cl Cl MeCF₃ i-Pr Me Br Me CF₃ i-Pr Cl Br Me CF₃ t-Bu Me H Me CF₃ t-Bu Cl H MeCF₃ t-Bu Me Cl Me CF₃ t-Bu Cl Cl Me CF₃ t-Bu Me Br Me CF₃ t-Bu Cl Br MeCF₃ Et Me H Me CF₃ Et Cl H Me CF₃ Et Me Cl Me CF₃ Et Cl Cl Me CF₃ Et MeBr Me CF₃ Et Cl Br Me CF₃ Me Me H Me CF₃ Me Cl H Me CF₃ Me Me Cl Me CF₃Me Cl Cl Me CF₃ Me Me Br Me CF₃ Me Cl Br Me CF₃ H Me H Me OCF₃ H Cl H MeOCF₃ H Me Cl Me OCF₃ H Cl Cl Me OCF₃ H Me Br Me OCF₃ H Cl Br Me OCF₃i-Pr Me H Me OCF₃ i-Pr Cl H Me OCF₃ i-Pr Me Cl Me OCF₃ i-Pr Cl Cl MeOCF₃ i-Pr Me Br Me OCF₃ i-Pr Cl Br Me OCF₃ t-Bu Me H Me OCF₃ t-Bu Cl HMe OCF₃ t-Bu Me Cl Me OCF₃ t-Bu Cl Cl Me OCF₃ t-Bu Me Br Me OCF₃ t-Bu ClBr Me OCF₃ Et Me H Me OCF₃ Et Cl H Me OCF₃ Et Me Cl Me OCF₃ Et Cl Cl MeOCF₃ Et Me Br Me OCF₃ Et Cl Br Me OCF₃ Me Me H Me OCF₃ Me Cl H Me OCF₃Me Me Cl Me OCF₃ Me Cl Cl Me OCF₃ Me Me Br Me OCF₃ Me Cl Br Me OCF₃ H MeH Me CF(CF₃)₂ H Cl H Me CF(CF₃)₂ H Me Cl Me CF(CF₃)₂ H Cl Cl Me CF(CF₃)₂H Me Br Me CF(CF₃)₂ H Cl Br Me CF(CF₃)₂ i-Pr Me H Me CF(CF₃)₂ i-Pr Cl HMe CF(CF₃)₂ i-Pr Me Cl Me CF(CF₃)₂ i-Pr Cl Cl Me CF(CF₃)₂ i-Pr Me Br MeCF(CF₃)₂ i-Pr Cl Br Me CF(CF₃)₂ t-Bu Me H Me CF(CF₃)₂ t-Bu Cl H MeCF(CF₃)₂ t-Bu Me Cl Me CF(CF₃)₂ t-Bu Cl Cl Me CF(CF₃)₂ t-Bu Me Br MeCF(CF₃)₂ t-Bu Cl Br Me CF(CF₃)₂ Et Me H Me CF(CF₃)₂ Et Cl H Me CF(CF₃)₂Et Me Cl Me CF(CF₃)₂ Et Cl Cl Me CF(CF₃)₂ Et Me Br Me CF(CF₃)₂ Et Cl BrMe CF(CF₃)₂ Me Me H Me CF(CF₃)₂ Me Cl H Me CF(CF₃)₂ Me Me Cl Me CF(CF₃)₂Me Cl Cl Me CF(CF₃)₂ Me Me Br Me CF(CF₃)₂ Me Cl Br Me CF(CF₃)₂

TABLE 5

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl i-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me HCl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br ClCl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cli-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-BuMe Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me HCl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et ClBr Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me MeBr Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl ClBr Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-PrMe Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me HBr Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L is CH₂CH₂ H Me H CF₃Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl BrCF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl ClCF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl HCF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl BrCF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et Cl Cl CF₃ Cl EtMe Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me H Cl Cl H Cl HCl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me HCl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cli-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-BuCl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H ClCl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me HCl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me ClBr Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl Br Cl H Me BrBr Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr Me Cl Br Cli-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H Br Cl t-BuCl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Cl t-Bu Cl BrBr Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl Br Cl Et Me BrBr Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl Br Cl Me Cl ClBr Cl Me Me Br Br Cl Me Cl Br Br Cl

TABLE 6

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me HCl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br ClCl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cli-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-BuMe Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me HCl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et ClBr Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me MeBr Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl ClBr Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-PrMe Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me HBr Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L is CH₂CH₂ H Me H CF₃Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl BrCF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl ClCF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl HCF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl BrCF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et Cl Cl CF₃ Cl EtMe Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me H Cl Cl H Cl HCl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me HCl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cli-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-BuCl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H ClCl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me HCl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me ClBr Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl Br Cl H Me BrBr Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr Me Cl Br Cli-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H Br Cl t-BuCl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Cl t-Bu Cl BrBr Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl Br Cl Et Me BrBr Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl Br Cl Me Cl ClBr Cl Me Me Br Br Cl Me Cl Br Br Cl

TABLE 7

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me HCl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br ClCl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cli-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-BuMe Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me HCl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et ClBr Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me MeBr Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl ClBr Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-PrMe Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me HBr Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl i-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L is CH₂CH₂ H Me H CF₃Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl BrCF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl ClCF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl HCF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl BrCF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et Cl Cl CF₃ Cl EtMe Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me H Cl Cl H Cl HCl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me HCl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cli-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-BuCl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H ClCl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me HCl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me ClBr Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl Br Cl H Me BrBr Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr Me Cl Br Cli-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H Br Cl t-BuCl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Cl t-Bu Cl BrBr Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl Br Cl Et Me BrBr Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl Br Cl Me Cl ClBr Cl Me Me Br Br Cl Me Cl Br Br Cl

TABLE 8

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me CNCF₃ Cl Me Me CN CF₃ Cl i-Pr Me CN CF₃ Cl H Me CN CF₃ F Me Me CN CF₃ Fi-Pr Me CN CF₃ F H Br F CF₃ Cl Me Br F CF₃ Cl i-Pr Br F CF₃ Cl H Br FCF₃ F Me Br F CF₃ F i-Pr Br F CF₃ F H Me H Cl Cl H Cl H Cl Cl H Me Cl ClCl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl HCl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br ClCl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Clt-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me ClCl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl HCl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H MeCN Cl Cl Me Me CN Cl Cl i-Pr Me CN Cl Cl H Me CN Cl F Me Me CN Cl F i-PrMe CN Cl F H Br F Cl Cl Me Br F Cl Cl i-Pr Br F Cl Cl H Br F Cl F Me BrF Cl F i-Pr Br F Cl F H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl BrCl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr MeCl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H BrCl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl H Me CN Br Cl Me Me CNBr Cl i-Pr Me CN Br Cl H Me CN Br F Me Me CN Br F i-Pr Me CN Br F H Br FBr Cl Me Br F Br Cl i-Pr Br F Br Cl H Br F Br F Me Br F Br F i-Pr Br FBr F L is CH₂CH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-PrMe Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-BuMe H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu MeBr CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me ClH CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ ClH Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H ClBr Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl ClCl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Clt-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl EtMe H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl EtCl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl MeMe Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H ClCl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cli-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-BuMe H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me BrBr Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et ClCl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me MeCl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl

TABLE 9

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me HCl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br ClCl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cli-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-BuMe Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me HCl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et ClBr Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me MeBr Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl ClBr Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-PrMe Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me HBr Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L is CH₂CH₂ H Me H CF₃Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl BrCF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl ClCF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl HCF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl BrCF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et Cl Cl CF₃ Cl EtMe Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me H Cl Cl H Cl HCl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me HCl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cli-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-BuCl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H ClCl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me HCl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me ClBr Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl Br Cl H Me BrBr Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr Me Cl Br Cli-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H Br Cl t-BuCl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Cl t-Bu Cl BrBr Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl Br Cl Et Me BrBr Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl Br Cl Me Cl ClBr Cl Me Me Br Br Cl Me Cl Br Br Cl

TABLE 10

R³ R^(4a) R^(4b) R⁵ R⁶ L is C═O H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr ClH CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr ClBr CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl ClCF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ ClEt Me Cl CF₃ Cl Et Cl Cl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me HCF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl MeCl Br CF₃ Cl H Me H Cl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H MeBr Cl Cl H Cl Br Cl Cl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cli-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-BuCl H Cl Cl t-Bu Me Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl BrCl Cl Et Me H Cl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me BrCl Cl Et Cl Br Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl ClCl Cl Me Me Br Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl BrCl H Cl Cl Br Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl HBr Cl i-Pr Me Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br BrCl t-Bu Me H Br Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Clt-Bu Me Br Br Cl t-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me ClBr Cl Et Cl Cl Br Cl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl HBr Cl Me Me Cl Br Cl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L isCH₂ H Me H CF₃ Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me BrCF₃ Cl H Cl Br CF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃Cl i-Pr Cl Cl CF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃Cl t-Bu Cl H CF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃Cl t-Bu Cl Br CF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et ClCl CF₃ Cl Et Me Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ ClMe Me Cl CF₃ Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me HCl Cl H Cl H Cl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br ClCl i-Pr Me H Cl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cli-Pr Me Br Cl Cl i-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-BuMe Cl Cl Cl t-Bu Cl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me HCl Cl Et Cl H Cl Cl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et ClBr Cl Cl Me Me H Cl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me MeBr Cl Cl Me Cl Br Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl ClBr Cl H Me Br Br Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-PrMe Cl Br Cl i-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me HBr Cl t-Bu Cl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Clt-Bu Cl Br Br Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl BrCl Et Me Br Br Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl BrCl Me Cl Cl Br Cl Me Me Br Br Cl Me Cl Br Br Cl L is CH₂CH₂ H Me H CF₃Cl H Cl H CF₃ Cl H Me Cl CF₃ Cl H Cl Cl CF₃ Cl H Me Br CF₃ Cl H Cl BrCF₃ Cl i-Pr Me H CF₃ Cl i-Pr Cl H CF₃ Cl i-Pr Me Cl CF₃ Cl i-Pr Cl ClCF₃ Cl i-Pr Me Br CF₃ Cl i-Pr Cl Br CF₃ Cl t-Bu Me H CF₃ Cl t-Bu Cl HCF₃ Cl t-Bu Me Cl CF₃ Cl t-Bu Cl Cl CF₃ Cl t-Bu Me Br CF₃ Cl t-Bu Cl BrCF₃ Cl Et Me H CF₃ Cl Et Cl H CF₃ Cl Et Me Cl CF₃ Cl Et Cl Cl CF₃ Cl EtMe Br CF₃ Cl Et Cl Br CF₃ Cl Me Me H CF₃ Cl Me Cl H CF₃ Cl Me Me Cl CF₃Cl Me Cl Cl CF₃ Cl Me Me Br CF₃ Cl Me Cl Br CF₃ Cl H Me H Cl Cl H Cl HCl Cl H Me Cl Cl Cl H Cl Cl Cl Cl H Me Br Cl Cl H Cl Br Cl Cl i-Pr Me HCl Cl i-Pr Cl H Cl Cl i-Pr Me Cl Cl Cl i-Pr Cl Cl Cl Cl i-Pr Me Br Cl Cli-Pr Cl Br Cl Cl t-Bu Me H Cl Cl t-Bu Cl H Cl Cl t-Bu Me Cl Cl Cl t-BuCl Cl Cl Cl t-Bu Me Br Cl Cl t-Bu Cl Br Cl Cl Et Me H Cl Cl Et Cl H ClCl Et Me Cl Cl Cl Et Cl Cl Cl Cl Et Me Br Cl Cl Et Cl Br Cl Cl Me Me HCl Cl Me Cl H Cl Cl Me Me Cl Cl Cl Me Cl Cl Cl Cl Me Me Br Cl Cl Me ClBr Cl Cl H Me H Br Cl H Cl H Br Cl H Me Cl Br Cl H Cl Cl Br Cl H Me BrBr Cl H Cl Br Br Cl i-Pr Me H Br Cl i-Pr Cl H Br Cl i-Pr Me Cl Br Cli-Pr Cl Cl Br Cl i-Pr Me Br Br Cl i-Pr Cl Br Br Cl t-Bu Me H Br Cl t-BuCl H Br Cl t-Bu Me Cl Br Cl t-Bu Cl Cl Br Cl t-Bu Me Br Br Cl t-Bu Cl BrBr Cl Et Me H Br Cl Et Cl H Br Cl Et Me Cl Br Cl Et Cl Cl Br Cl Et Me BrBr Cl Et Cl Br Br Cl Me Me H Br Cl Me Cl H Br Cl Me Me Cl Br Cl Me Cl ClBr Cl Me Me Br Br Cl Me Cl Br Br ClFormulation/Utility

Compounds of this invention will generally be used as a formulation orcomposition with an agriculturally suitable carrier comprising at leastone of a liquid diluent, a solid diluent or a surfactant. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature. Useful formulations include liquids such as solutions(including emulsifiable concentrates), suspensions, emulsions (includingmicroemulsions and/or suspoemulsions) and the like which optionally canbe thickened into gels. Useful formulations further include solids suchas dusts, powders, granules, pellets, tablets, films, and the like whichcan be water-dispersible (“wettable”) or water-soluble. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. Sprayableformulations can be extended in suitable media and used at spray volumesfrom about one to several hundred liters per hectare. High-strengthcompositions are primarily used as intermediates for furtherformulation.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges that add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand 5-90  0-94 1-15 Water-soluble Granules, Tablets and Powders.Suspensions, Emulsions, 5-50 40-95 0-15 Solutions (includingEmulsifiable Concentrates) Dusts 1-25 70-99 0-5  Granules and Pellets0.01-99      5-99.99 0-15 High Strength Compositions 90-99   0-10 0-2 

Typical solid diluents are described in Watkins, et al., Handbook ofInsecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books,Caldwell, N.J. Typical liquid diluents are described in Marsden,Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon'sDetergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J.,as well as Sisely and Wood, Encyclopedia of Surface Active Agents,Chemical Publ. Co., Inc., New York, 1964, list surfactants andrecommended uses. All formulations can contain minor amounts ofadditives to reduce foam, caking, corrosion, microbiological growth andthe like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols,polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acidesters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzenesulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates,naphthalene sulfonate formaldehyde condensates, polycarboxylates, andpolyoxyethylene/polyoxypropylene block copolymers. Solid diluentsinclude, for example, clays such as bentonite, montmorillonite,attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth,urea, calcium carbonate, sodium carbonate and bicarbonate, and sodiumsulfate. Liquid diluents include, for example, water,N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethyleneglycol, polypropylene glycol, paraffins, alkylbenzenes,alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn,peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol,cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. Dusts and powders can be prepared byblending and, usually, grinding as in a hammer mill or fluid-energymill. Suspensions are usually prepared by wet-milling; see, for example,U.S. Pat. No. 3,060,084. Granules and pellets can be prepared byspraying the active material upon preformed granular carriers or byagglomeration techniques. See Browning, “Agglomeration”, ChemicalEngineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer'sHandbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 andfollowing, and PCT Publication WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook,8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Table A.

EXAMPLE A

Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodiumligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite(calcined) 23.0%.

EXAMPLE B

Granule

Compound 1 10.0% attapulgite granules (low volatile matter, 90.0%.0.71/0.30 mm; U.S.S. No. 25-50 sieves)

EXAMPLE C

Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calciumligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%.

EXAMPLE D

Emulsifiable Concentrate

Compound 1 20.0% blend of oil soluble sulfonates 10.0% andpolyoxyethylene ethers isophorone 70.0%.

EXAMPLE E

Granule

Compound 1 0.5% cellulose 2.5% lactose 4.0% cornmeal 93.0%.

Compounds of this invention are characterized by favorable metabolicand/or soil residual patterns and exhibit activity controlling aspectrum of agronomic and non-agronomic invertebrate pests. (In thecontext of this disclosure “invertebrate pest control” means inhibitionof invertebrate pest development (including mortality) that causessignificant reduction in feeding or other injury or damage caused by thepest; related expressions are defined analogously.) As referred to inthis disclosure, the term “invertebrate pest” includes arthropods,gastropods and nematodes of economic importance as pests. The term“arthropod” includes insects, mites, spiders, scorpions, centipedes,millipedes, pill bugs and symphylans. The term “gastropod” includessnails, slugs and other Stylommatophora. The term “nematode” includesall of the helminths, such as: roundworms, heartworms, and phytophagousnematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms(Cestoda). Those skilled in the art will recognize that not allcompounds are equally effective against all pests. Compounds of thisinvention display activity against economically important agronomic andnonagronomic pests. The term “agronomic” refers to the production offield crops such as for food and fiber and includes the growth of cerealcrops (e.g., wheat, oats, barley, rye, rice, maize), soybeans, vegetablecrops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweetpotatoes, grapes, cotton, and tree fruits (e.g., pome fruits, stonefruits and citrus fruits). The term “nonagronomic” refers to otherhorticultural (e.g., forest, greenhouse, nursery or ornamental plantsnot grown in a field), public (human) and animal health, domestic andcommercial structure, household, and stored product applications orpests. For reason of invertebrate pest control spectrum and economicimportance, protection (from damage or injury caused by invertebratepests) of agronomic crops of cotton, maize, soybeans, rice, vegetablecrops, potato, sweet potato, grapes and tree fruit by controllinginvertebrate pests are preferred embodiments of the invention. Agronomicor nonagronomic pests include larvae of the order Lepidoptera, such asarmyworms, cutworms, loopers, and heliothines in the family Noctuidae(e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm(Spodoptera exigua Hübner), black cutworm (Agrotis ipsilon Hufnagel),cabbage looper (Trichoplusia ni Hübner), tobacco budworm (Heliothisvirescens Fabricius)); borers, casebearers, webworms, coneworms,cabbageworms and skeletonizers from the family Pyralidae (e.g., Europeancorn borer (Ostrinia nubilalis Hübner), navel orangeworm (Amyeloistransitella Walker), corn root webworm (Crambus caliginosellus Clemens),sod webworm (Herpetogramma licarsisalis Walker)); leafrollers, budworms,seed worms, and fruit worms in the family Tortricidae (e.g., codlingmoth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteanaClemens), oriental fruit moth (Grapholita molesta Busck)); and manyother economically important lepidoptera (e.g., diamondback moth(Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiellaSaunders), gypsy moth (Lymantria dispar Linnaeus)); nymphs and adults ofthe order Blattodea including cockroaches from the families Blattellidaeand Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus),Asian cockroach (Blatella asahinai Mizukubo), German cockroach(Blattella germanica Linnaeus), brownbanded cockroach (Supellalongipalpa Fabricius), American cockroach (Periplaneta americanaLinnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeiracockroach (Leucophaea maderae Fabricius)); foliar feeding larvae andadults of the order Coleoptera including weevils from the familiesAnthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomusgrandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel),granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilusoryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leafbeetles, potato beetles, and leafminers in the family Chrysomelidae(e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), westerncorn rootworm (Diabrotica virgifera virgifera LeConte)); chafers andother beetles from the family Scaribaeidae (e.g., Japanese beetle(Popillia japonica Newman) and European chafer (Rhizotrogus majalisRazoumowsky)); carpet beetles from the family Dermestidae; wirewormsfrom the family Elateridae; bark beetles from the family Scolytidae andflour beetles from the family Tenebrionidae. In addition it includes:adults and larvae of the order Dermaptera including earwigs from thefamily Forficulidae (e.g., European earwig (Forficula auriculariaLinnaeus), black earwig (Chelisoches morio Fabricius)); adults andnymphs of the orders Hemiptera and Homoptera such as, plant bugs fromthe family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.Empoasca spp.) from the family Cicadellidae, planthoppers from thefamilies Fulgoroidae and Delphacidae, treehoppers from the familyMembracidae, psyllids from the family Psyllidae, whiteflies from thefamily Aleyrodidae, aphids from the family Aphididae, phylloxera fromthe family Phylloxeridae, mealybugs from the family Pseudococcidae,scales from the families Coccidae, Diaspididae and Margarodidae, lacebugs from the family Tingidae, stink bugs from the family Pentatomidae,cinch bugs (e.g., Blissus spp.) and other seed bugs from the familyLygaeidae, spittlebugs from the family Cercopidae squash bugs from thefamily Coreidae, and red bugs and cotton stainers from the familyPyrrhocoridae. Also included are adults and larvae of the order Acari(mites) such as spider mites and red mites in the family Tetranychidae(e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite(Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieliMcGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flatmite (Brevipalpus lewisi McGregor)), rust and bud mites in the familyEriophyidae and other foliar feeding mites and mites important in humanand animal health, i.e. dust mites in the family Epidermoptidae,follicle mites in the family Demodicidae, grain mites in the familyGlycyphagidae, ticks in the order Ixodidae (e.g., deer tick (Ixodesscapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann),American dog tick (Dermacentor variabilis Say), lone star tick(Amblyomma americanum Linnaeus) and scab and itch mites in the familiesPsoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures of theorder Orthoptera including grasshoppers, locusts and crickets (e.g.,migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M.differentialis Thomas), American grasshoppers (e.g., Schistocercaamericana Drury), desert locust (Schistocerca gregaria Forskal),migratory locust (Locusta migratoria Linnaeus), house cricket (Achetadomesticus Linnaeus), mole crickets (Gryllotalpa spp.)); adults andimmatures of the order Diptera including leafminers, midges, fruit flies(Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots,house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g.,Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g.,Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g.,Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies(e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.),cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.),keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes(e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g.,Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids,and other Nematocera; adults and immatures of the order Thysanopteraincluding onion thrips (Thrips tabaci Lindeman) and other foliar feedingthrips; insect pests of the order Hymenoptera including ants (e.g., redcarpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant(Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonisLinnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant(Solenopsis geminata Fabricius), red imported fire ant (Solenopsisinvicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant(Paratrechina longicornis Latreille), pavement ant (Tetramoriumcaespitum Linnaeus), cornfield ant (Lasius alienus Förster), odoroushouse ant (Tapinoma sessile Say)), bees (including carpenter bees),hornets, yellow jackets and wasps; insect pests of the order Isopteraincluding the eastern subterranean termite (Reticulitermes flavipesKollar), western subterranean termite (Reticulitermes hesperus Banks),Formosan subterranean termite (Coptotermes formosanus Shiraki), WestIndian drywood termite (Incisitermes immigrans Snyder) and othertermites of economic importance; insect pests of the order Thysanurasuch as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobiadomestica Packard); insect pests of the order Mallophaga and includingthe head louse (Pediculus humanus capitis De Geer), body louse(Pediculus humanus humanus Linnaeus), chicken body louse (Menacanthusstramineus Nitszch), dog biting louse (Trichodectes canis De Geer),fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicolaovis Schrank), short-nosed cattle louse (Haematopinus eurysternusNitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) andother sucking and chewing parasitic lice that attack man and animals;insect pests of the order Siphonoptera including the oriental rat flea(Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felisBouche), dog flea (Ctenocephalides canis Curtis), hen flea(Ceratophyllus gallinae Schrank), sticktight flea (Echidnophagagallinacea Westwood), human flea (Pulex irritans Linnaeus) and otherfleas afflicting mammals and birds. Additional arthropod pests coveredinclude: spiders in the order Araneae such as the brown recluse spider(Loxosceles reclusa Gertsch & Mulaik) and the black widow spider(Latrodectus mactans Fabricius), and centipedes in the orderScutigeromorpha such as the house centipede (Scutigera coleoptrataLinnaeus). Activity also includes members of the Classes Nematoda,Cestoda, Trematoda, and Acanthocephala including economically importantmembers of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida,Spirurida, and Enoplida such as but not limited to economicallyimportant agricultural pests (i.e. root knot nematodes in the genusMeloidogyne, lesion nematodes in the genus Pratylenchus, stubby rootnematodes in the genus Trichodorus, etc.) and animal and human healthpests (i.e. all economically important flukes, tapeworms, androundworms, such as Strongylus vulgaris in horses, Toxocara canis indogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs,Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus inruminants, etc.).

Compounds of the invention show particularly high activity against pestsin the order Lepidoptera (e.g., Alabama argillacea Hübner (cotton leafworm), Archips argyrospila Walker (fruit tree leaf roller), A. rosanaLinnaeus (European leaf roller) and other Archips species, Chilosuppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee(rice leaf roller), Crambus caliginosellus Clemens (corn root webworm),Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonellaLinnaeus (codling moth), Earias insulana Boisduval (spiny bollworm),Earias vittella Fabricius (spotted bollworm), Helicoverpa armigeraHübner (American bollworm), Helicoverpa zea Boddie (corn earworm),Heliothis virescens Fabricius (tobacco budworm), Herpetogrammalicarsisalis Walker (sod webworm), Lobesia botrana Denis &Schiffermüller (grape berry moth), Pectinophora gossypiella Saunders(pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer),Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus(small white butterfly), Plutella xylostella Linnaeus (diamondbackmoth), Spodoptera exigua Hübner (beet armyworm), Spodoptera lituraFabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperdaJ. E. Smith (fall armyworm), Trichoplusia ni Hübner (cabbage looper) andTuta absoluta Meyrick (tomato leafminer)). Compounds of the inventionalso have commercially significant activity on members from the orderHomoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphiscraccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid),Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer(apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solaniKaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell(strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheataphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosomalanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy(mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid),Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiaeThomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, greenpeach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigusspp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (cornleaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid),Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius(English grain aphid), Therioaphis maculata Buckton (spotted alfalfaaphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid),and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp.(adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisiatabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisiaargentifoli Bellows & Perring (silverleaf whitefly), Dialeurodes citriAshmead (citrus whitefly) and Trialeurodes vaporariorum Westwood(greenhouse whitefly); Empoasca fabae Harris (potato leafhopper),Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler(green leafhopper), Nephotettix nigropictus Stål (rice leafhopper),Nilaparvata lugens Stål (brown planthopper), Peregrinus maidis Ashmead(corn planthopper), Sogatella furcifera Horvath (white-backedplanthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocybapomaria McAtee white apple leafhopper, Erythroneoura spp. (grapeleafhoppers); Magicidada septendecim Linnaeus (periodical cicada);Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrusmealybug); Pseudococcus spp. (other mealybug complex); Cacopsyllapyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmonpsylla). These compounds also have activity on members from the orderHemiptera including: Acrosternum hilare Say (green stink bug), Anasatristis De Geer (squash bug), Blissus leucopterus leucopterus Say(chinch bug), Corythuca gossypii Fabricius (cotton lace bug),Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellusHerrich-Schäffer (cotton stainer), Euchistus servus Say (brown stinkbug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug),Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say(leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois(tarnished plant bug), Nezara viridula Linnaeus (southern green stinkbug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatusDallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cottonfleahopper). Other insect orders controlled by compounds of theinvention include Thysanoptera (e.g., Frankliniella occidentalisPergande (western flower thrip), Scirthothrips citri Moulton (citrusthrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaciLindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsadecemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant(Mexican bean beetle) and wireworms of the genera Agriotes, Athous orLimonius).

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, growth regulatorssuch as rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum ofagricultural utility. Thus compositions of the present invention canfurther comprise a biologically effective amount of at least oneadditional biologically active compound or agent. Examples of suchbiologically active compounds or agents with which compounds of thisinvention can be formulated are: insecticides such as abamectin,acephate, acetamiprid, avermectin, azadirachtin, azinphos-methyl,bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan,emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb,fenoxycarb, fenpropathrin, fenproximate, fenvalerate, fipronil,flonicamid, flucythrinate, tau-fluvalinate, flufenoxuron, fonophos,halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos,lufenuron, malathion, metaldehyde, methamidophos, methidathion,methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide,nithiazin, novaluron, oxamyl, parathion, parathion-methyl, permethrin,phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos,pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, sulprofos,tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin,trichlorfon and triflumuron; fungicides such as acibenzolar,azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic coppersulfate), bromuconazole, carpropamid, captafol, captan, carbendazim,chloroneb, chlorothalonil, copper oxychloride, copper salts,cyflufenamid, cymoxanil, cyproconazole, cyprodinil,(S)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH 7281), diclocymet (S-2900), diclomezine, dicloran, difenoconazole,(S)-3,5-dihydro-5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one(RP 407213), dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil,flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil,flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658),hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane,kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil,metalaxyl, metconazole, metomino-strobin/fenominostrobin (SSF-126),myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl,penconazole, pencycuron, probenazole, prochloraz, propamocarb,propiconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon,quinoxyfen, spiroxamine, sulfur, tebuconazole, tetraconazole,thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil,triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole,validamycin and vinclozolin; nematocides such as aldicarb, oxamyl andfenamiphos; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; andbiological agents such as Bacillus thuringiensis including ssp. aizawaiand kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, andentomopathogenic bacteria, virus and fungi.

A general reference for these agricultural protectants is The PesticideManual, 12th Edition, C. D. S. Tomlin, Ed., British Crop ProtectionCouncil, Farnham, Surrey, U.K., 2000.

Preferred insecticides and acaricides for mixing with compounds of thisinvention include pyrethroids such as cypermethrin, cyhalothrin,cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate andtralomethrin; carbamates such as fenothicarb, methomyl, oxamyl andthiodicarb; neonicotinoids such as clothianidin, imidacloprid andthiacloprid; neuronal sodium channel blockers such as indoxacarb;insecticidal macrocyclic lactones such as spinosad, abamectin,avermectin and emamectin; γ-aminobutyric acid (GABA) antagonists such asendosulfan, ethiprole and fipronil; insecticidal ureas such asflufenoxuron and triflumuron; juvenile hormone mimics such as diofenolanand pyriproxyfen; pymetrozine; and amitraz. Preferred biological agentsfor mixing with compounds of this invention include Bacillusthuringiensis and Bacillus thuringiensis delta endotoxin as well asnaturally occurring and genetically modified viral insecticidesincluding members of the family Baculoviridae as well as entomophagousfungi.

Most preferred mixtures include a mixture of a compound of thisinvention with cyhalothrin; a mixture of a compound of this inventionwith beta-cyfluthrin; a mixture of a compound of this invention withesfenvalerate; a mixture of a compound of this invention with methomyl;a mixture of a compound of this invention with imidacloprid; a mixtureof a compound of this invention with thiacloprid; a mixture of acompound of this invention with indoxacarb; a mixture of a compound ofthis invention with abamectin; a mixture of a compound of this inventionwith endosulfan; a mixture of a compound of this invention withethiprole; a mixture of a compound of this invention with fipronil; amixture of a compound of this invention with flufenoxuron; a mixture ofa compound of this invention with pyriproxyfen; a mixture of a compoundof this invention with pymetrozine; a mixture of a compound of thisinvention with amitraz; a mixture of a compound of this invention withBacillus thuringiensis and a mixture of a compound of this inventionwith Bacillus thuringiensis delta endotoxin.

In certain instances, combinations with other invertebrate pest controlcompounds or agents having a similar spectrum of control but a differentmode of action will be particularly advantageous for resistancemanagement. Thus, compositions of the present invention can furthercomprise a biologically effective amount of at least one additionalinvertebrate pest control compound or agent having a similar spectrum ofcontrol but a different mode of action. Contacting a plant geneticallymodified to express a plant protection compound (e.g., protein) or thelocus of the plant with a biologically effective amount of a compound ofinvention can also provide a broader spectrum of plant protection and beadvantageous for resistance management.

Invertebrate pests are controlled in agronomic and nonagronomicapplications by applying one or more of the compounds of this invention,in an effective amount, to the environment of the pests including theagronomic and/or nonagronomic locus of infestation, to the area to beprotected, or directly on the pests to be controlled. Thus, the presentinvention further comprises a method for the control of invertebrates inagronomic and/or nonagronomic applications, comprising contacting theinvertebrates or their environment with a biologically effective amountof one or more of the compounds of the invention, or with a compositioncomprising at least one such compound or a composition comprising atleast one such compound and an effective amount of at least oneadditional biologically active compound or agent.

A preferred method of contact is by spraying. Alternatively, a granularcomposition comprising a compound of the invention can be applied to theplant foliage or the soil. Compounds of this invention are alsoeffectively delivered through plant uptake by contacting the plant witha composition comprising a compound of this invention applied as a soildrench of a liquid formulation, a granular formulation to the soil, anursery box treatment or a dip of transplants. Compounds are alsoeffective by topical application of a composition comprising a compoundof this invention to the locus of infestation. Other methods of contactinclude application of a compound or a composition of the invention bydirect and residual sprays, aerial sprays, seed coatings,microencapsulations, systemic uptake, baits, eartags, boluses, foggers,fumigants, aerosols, dusts and many others.

The compounds of this invention can be incorporated into baits that areconsumed by the invertebrates or within devices such as traps and thelike. Granules or baits comprising between 0.01-5% active ingredient,0.05-10% moisture retaining agent(s) and 40-99% vegetable flour areeffective in controlling soil insects at very low application rates,particularly at doses of active ingredient that are lethal by ingestionrather than by direct contact.

The compounds of this invention can be applied in their pure state, butmost often application will be of a formulation comprising one or morecompounds with suitable carriers, diluents, and surfactants and possiblyin combination with a food depending on the contemplated end use. Apreferred method of application involves spraying a water dispersion orrefined oil solution of the compounds. Combinations with spray oils,spray oil concentrations, spreader stickers, adjuvants, other solvents,and synergists such as piperonyl butoxide often enhance compoundefficacy.

The rate of application required for effective control (i.e.“biologically effective amount”) will depend on such factors as thespecies of invertebrate to be controlled, the pest's life cycle, lifestage, its size, location, time of year, host crop or animal, feedingbehavior, mating behavior, ambient moisture, temperature, and the like.Under normal circumstances, application rates of about 0.01 to 2 kg ofactive ingredient per hectare are sufficient to control pests inagronomic ecosystems, but as little as 0.0001 kg/hectare may besufficient of as much as 8 kg/hectare may be required. For nonagronomicapplications, effective use rates will range from about 1.0 to 50mg/square meter but as little as 0.1 mg/square meter may be sufficientor as much as 150 mg/square meter may be required. One skilled in theart can easily determine the biologically effective amount necessary forthe desired level of invertebrate pest control.

The following Tests in the Biological Examples of the Inventiondemonstrate the efficacy of methods of the invention for protectingplants from specific arthropod pests. “Control efficacy” representsinhibition of arthropod development (including mortality) that causessignificantly reduced feeding. The pest control protection afforded bythe compounds is not limited, however, to these species. See IndexTables A-D for compound descriptions. The following abbreviations areused in the Index Tables that follow: t is tertiary, n is normal, i isiso, s is secondary, c is cyclo, Me is methyl, Et is ethyl, Pr is propyland Bu is butyl; accordingly i-Pr is isopropyl, s-Bu is secondary butyl,etc. The abbreviation “Ex.” stands for “Example” and is followed by anumber indicating in which example the compound is prepared.

INDEX TABLE A

Compound R³ R^(4a) R^(4b) R⁵ m.p. (° C.) 1 i-Pr Me H CF₃ * 2 Me Me BrCF₃ * 3 i-Pr Me Br CF₃ * 4 t-Bu Me Br CF₃ * 5 Me Me Br Br * 6 (Ex. 1)i-Pr Me Br Br * *See Index Table D for ¹H NMR data.

INDEX TABLE B

Compound R³ R^(4a) R^(4b) R⁵ R¹³ m.p. (° C.) 7 (Ex. 2) i-Pr Me H Br H * 8 i-Pr Cl Cl Cl H 192-194  9 i-Pr Cl Cl Br H 207-208 10 i-Pr Cl Cl CF₃H 167-168 11 Me Cl Cl Cl H 173-178 12 Me Cl Cl Br H 200-202 13 Me Cl ClCF₃ H 157-158 14 i-Pr Me Cl Cl H 219-220 15 i-Pr Me Cl Br H 228-231 16i-Pr Me Cl CF₃ H 213-214 17 Me Me Cl Cl H 238-240 18 Me Me Cl Br H254-255 19 Me Me Cl CF₃ H 207-208 20 i-Pr Me H Cl CO₂H 143-190 21 Me ClCl Cl CO₂H * 22 Cl Cl Cl Cl 3-pyridyl 135-156 23 Cl Cl Cl Cl2-imidazolyl * 24 Cl Cl Cl Cl 4-imidazolyl * 25 Me Cl Cl Cl CO₂Et * 26Me Cl Cl Cl CH₂CO₂Me * 27 Me Cl Cl Cl 4-(CO₂Me)Ph 178-232 28 H Cl Cl ClH 181-192 29 H Cl Cl CF₃ H 162-177 *See Index Table D for ¹H NMR data.

INDEX TABLE C

Compound R³ R^(4a) R^(4b) R⁵ m.p. (° C.) 30 H Cl Cl Cl * 31 H Cl ClCF₃ * *See Index Table D for ¹H NMR data.

INDEX TABLE D Cmpd No. ¹H NMR Data (CDCl₃ solution unless indicatedotherwise)^(a) 1 DMSO-d₆ 8.6-8.5(dd, 1H), 8.4(dd, 1H), 8.29(s, 1H),8.0(d, 1H), 7.8(dd, 1H), 7.6(d, 1H), 7.4-7.3(t, 1H), 5.0(m, 1H), 2.08(s,3H), 1.41(d, 6H). 2 8.41(dd, 1H), 8.21(d, 1H), 7.96(dd, 1H), 7.58(d,1H), 7.45(dd, 1H), 7.38(s, 1H), 3.40(s, 3H), 2.16(s, 3H). 3 8.36(dd,1H), 8.17(d, 1H), 7.94(dd, 1H), 7.56(d, 1H), 7.42(dd, 1H), 7.37(s, 1H),5.08(m, 1H), 2.16(s, 3H), 1.46(d, 6H). 4 8.44(dd, 1H), 8.02(d, 1H),7.95(dd, 1H), 7.52(d, 1H), 7.45(dd, 1H), 7.28(s, 1H), 2.11(s, 3H),1.64(s, 9H). 5 8.39(dd, 1H), 8.20(d, 1H), 7.93(dd, 1H), 7.57(d, 1H),7.41(dd, 1H), 7.12(s, 1H), 3.40(s, 3H), 2.16(s, 3H). 6 8.34(dd, 1H),8.17(d, 1H), 7.91(dd, 1H), 7.54(d, 1H), 7.39(dd, 1H), 7.12(s, 1H),5.08(m, 1H), 2.17(s, 3H), 1.47(d, 6H). 7 8.3(m, 1H), 7.9-7.8(m, 2H),7.4-7.3(m, 3H), 6.0-5.9(s, 1H), 5.9(d, 1H), 5.0-4.8(m, 1H), 4.4-4.3(d,1H), 2.10(s, 3H), 1.3-1.1(m, 6H) 21 DMSO-d₆ 8.50(dd, 1H), 8.21(d, 1H),7.87-7.75(m, 2H), 7.61(ddd, 1H), 5.83(bs, 1H), 3.01(s, 3H) 23 DMSO-d₆8.38(d, 1H), 8.22(bs, 1H), 7.9-7.7(bm, 2H), 7.58(t, 1H), 7.16-7.05(m,2H), 6.83(bs, 1H), 3.15(bs, 3H) 24 DMSO-d₆ 8.48(s, 1H), 8.24(d, 1H),7.87-7.77(m, 2H), 7.70(s, 1H), 7.61(m, 1H), 7.01(s, 2H), 6.90(s, 1H),3.18(bs, 3H) 25 DMSO-d₆ 8.4-8.2(b, 2H), 8.1-7.8(b, 2H), 7.55(b, 1H),7.2-7.1(m, 2H), 6.8-6.6(b, 1H), 4.3-3.9(b, 2H), 3.11(s, 3H), 1.2-0.9(b,3H) 26 DMSO-d₆ 8.30(d, 1H), 8.20(bs, 1H), 7.98(bs, 1H), 7.82(bs, 1H),7.55(t, 1H), 7.41(bs, 1H), 6.08(bs, 1H), 3.60(b, 2H), 3.04(s, 3H) 30DMSO-d₆ 8.27(dd, 1H), 8.09(s 1H), 8.07(dd 1H), 7.70(dd, 1H), 7.44(dd,1H), 7.17(s, 1H), 4.44(t, 2H), 3.99(t, 2H) 31 DMSO-d₆ 8.24(dd, 1H),8.03(dd 1H), 7.88(s, 1H), 7.66(s, 1H), 7.45(s, 1H), 7.40(s, 1H), 4.33(t,2H), 3.91(t, 2H) ^(a) ¹H NMR data are in ppm downfield fromtetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet,(t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets,(dt)-doublet of triplets, (br s)-broad singlet.

BIOLOGICAL EXAMPLES OF THE INVENTION Test A

For evaluating control of diamondback moth (Plutella xylostella) thetest unit consisted of a small open container with a 12-14-day-oldradish plant inside. This was pre-infested with 10-15 neonate larvae ona piece of insect diet by use of a core sampler to remove a plug from asheet of hardened insect diet having many larvae growing on it andtransfer the plug containing larvae and diet to the test unit. Thelarvae moved onto the test plant as the diet plug dried out.

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionicsurfactant containing alkylarylpolyoxyethylene, free fatty acids,glycols and isopropanol (Loveland Industries, Inc). The formulatedcompounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzlewith ⅛ JJ custom body (Spraying Systems Co.) positioned 1.27 cm (0.5inches) above the top of each test unit. All experimental compounds inthis screen were sprayed at 50 ppm and replicated three times. Afterspraying of the formulated test compound, each test unit was allowed todry for 1 hour and then a black, screened cap was placed on top. Thetest units were held for 6 days in a growth chamber at 25° C. and 70%relative humidity. Plant feeding damage was then visually assessed.

Of the compounds tested, the following provided excellent levels ofplant protection (20% or less feeding damage): 1, 2, 3, 5, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 22, 23, 24, 26, 28 and 29.

Test B

For evaluating control of fall armyworm (Spodoptera frugiperda) the testunit consisted of a small open container with a 4-5-day-old corn (maize)plant inside. This was pre-infested with 1-15 1-day-old larvae on apiece of insect diet by use of a core sampler as described for Test A.

Test compounds were formulated and sprayed at 50 ppm as described forTest A. The applications were replicated three times. After spraying,the test units were maintained in a growth chamber and then visuallyrated as described for Test A.

Of the compounds tested, the following provided excellent levels ofplant protection (20% or less feeding damage): 5, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 23, 24, 28 and 29.

Test C

For evaluating control of tobacco budworm (Heliothis virescens) the testunit consisted of a small open container with a 6-7 day old cotton plantinside. This was pre-infested with 8 2-day-old larvae on a piece ofinsect diet by use of a core sampler as described for Test A.

Test compounds were formulated and sprayed at 50 ppm as described forTest A. The applications were replicated three times. After spraying,the test units were maintained in a growth chamber and then visuallyrated as described for Test A.

Of the compounds tested, the following provided excellent levels ofplant protection (20% or less feeding damage): 1, 2, 5, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 21, 23 and 24.

Test D

For evaluating control of beet armyworm (Spodoptera exigua) the testunit consisted of a small open container with a 4-5-day-old corn plantinside. This was pre-infested with 10-15 1-day-old larvae on a piece ofinsect diet by use of a core sampler as described for Test A.

Test compounds were formulated and sprayed at 50 ppm as described forTest A. The applications were replicated three times. After spraying,the test units were maintained in a growth chamber and then visuallyrated as described for Test A.

Of the compounds tested, the following provided excellent levels ofplant protection (20% or less feeding damage): 2, 5, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 23 and 24.

Test E

For evaluating control of green peach aphid (Myzus persicae) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 12-15-day-old radish plant inside. This waspre-infested by placing on a leaf of the test plant 30-40 aphids on apiece of leaf excised from a culture plant (cut-leaf method). The larvaemoved onto the test plant as the leaf piece desiccated. Afterpre-infestation, the soil of the test unit was covered with a layer ofsand.

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionicsurfactant containing alkylarylpolyoxyethylene, free fatty acids,glycols and isopropanol (Loveland Industries, Inc.). The formulatedcompounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzlewith 1/8 JJ custom body (Spraying Systems Co.) positioned 1.27 cm (0.5inches) above the top of each test unit. All experimental compounds inthis screen were sprayed at 250 ppm and replicated three times. Afterspraying of the formulated test compound, each test unit was allowed todry for 1 hour and then a black, screened cap was placed on top. Thetest units were held for 6 days in a growth chamber at 19-21° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds tested, the following resulted in at least 80%mortality: 8, 9, 11, 12, 13, 19, 28 and 29.

Test F

For evaluating control of cotton melon aphid (Aphis gossypii) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 6-7-day-old cotton plant inside. This was pre-infestedwith 30-40 aphids on a piece of leaf according to the cut-leaf methoddescribed for Test E, and the soil of the test unit was covered with alayer of sand.

Test compounds were formulated and sprayed at 250 ppm as described forTest E. The applications were replicated three times. After spraying,the test units were maintained in a growth chamber and then visuallyrated as described for Test E.

Of the compounds tested, the following resulted in at least 80%mortality: 8, 9, 11, 12, 13, 15, 16, 19 and 29.

Test G

For evaluating control of Corn Planthopper (Peregrinus maidis) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 3-4 day old corn (maize) plant (spike) inside. Whitesand was added to the top of the soil prior to application. Testcompounds were formulated and sprayed at 250 ppm and replicated threetimes as described for Test E. After spraying, the test units wereallowed to dry for 1 hour before they were post-infested with 10-20 CornPlanthoppers (18 to 20 day old nymphs) by sprinkling them onto the sandwith a salt shaker. A black, screened cap is placed on the top of thecylinder. The test units were held for 6 days in a growth chamber at19-21° C. and 50-70% relative humidity. Each test unit was then visuallyassessed for insect mortality.

Of the compounds tested, the following resulted in at least 80%mortality: 12 and 13.

Test H

For evaluating control of Potato Leafhopper (Empoasca fabae Harris)through contact and/or systemic means, the test unit consisted of asmall open container with a 5-6 day old Longio bean plant (primaryleaves emerged) inside. White sand was added to the top of the soil andone of the primary leaves was excised prior to application. Testcompounds were formulated and sprayed at 250 ppm and replicated threetimes as described for Test E. After spraying, the test units wereallowed to dry for 1 hour before they were post-infested with 5 PotatoLeafhoppers (18 to 21 day old adults). A black, screened cap is placedon the top of the cylinder. The test units were held for 6 days in agrowth chamber at 19-21° C. and 50-70% relative humidity. Each test unitwas then visually assessed for insect mortality.

Of the compounds tested, the following resulted in at least 80%mortality: 8, 9, 10, 11, 12, 13, 15, 16, 19, 24 and 29.

1. A compound of Formula 6, an N-oxide or salt thereof,

wherein R³ is H, methyl or iso-propyl; n is 2; one R⁴ is in the2-position and is methyl; and the other R⁴ is in the 4-position and isCN.
 2. The compound of claim 1 wherein R³ is H.
 3. The compound of claim1 wherein R³ is methyl.
 4. The compound of claim 1 wherein R³ isiso-propyl.